Low molecular weight cellulose mixed esters and their use as low viscosity binders and modifiers in coating compositions

ABSTRACT

Cellulose mixed esters are disclosed having low molecular weights and low degrees of polymerization. These new cellulose mixed esters include cellulose acetate propionate and cellulose acetate butyrate. The esters exhibit solubility in a wide range of organic solvents with minimal viscosity increase, are compatible with a wide variety of resins, and are useful in coatings and inks compositions as binder resins and rheology modifiers.

RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.10/796,176, filed Mar. 9, 2004, which claims priority from U.S.Provisional Patent Application No. 60/455,033, filed Mar. 14, 2003, thedisclosure of which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

This invention belongs to the field of cellulose chemistry, and moreparticularly, to low molecular weight cellulose mixed esters that areuseful in coating and ink compositions as low viscosity binder resinsand rheology modifiers.

BACKGROUND OF THE INVENTION

Cellulose esters are valuable polymers that are useful in many plastic,film, coating, and fiber applications. Cellulose esters (CEs) aretypically synthesized by the reaction of cellulose with an anhydride oranhydrides corresponding to the desired ester group or groups, using thecorresponding carboxylic acid as diluent and product solvent. Some ofthese ester groups can afterward be hydrolyzed to obtain apartially-esterified product. These partially substituted celluloseesters have great commercial value, and find use in coatings, wheretheir greater solubility and compatibility with co-resins (in comparisonwith triesters) and hydroxyl group content (to facilitate crosslinking)are prized.

An important aspect in obtaining suitable cellulose esters hastraditionally been maintaining molecular weight during theesterification process. A loss in molecular weight is associated withpoor plastic properties and brittle films, a flexible film being thedesired goal. Thus, it has long been recognized that in order to obtaina suitable chloroform-soluble (triacetate) cellulose ester, theacetylation process must not result in significant degradation, orlowering of the molecular weight, of the cellulose. See, for example,U.S. Pat. No. 1,683,347.

When it was discovered that these early triacetate esters could bemodified, via partial hydrolysis of the acetate groups, to obtainacetone-soluble cellulose acetate, maintaining a suitable molecularweight during hydrolysis remained important. See, for example, U.S. Pat.No. 1,652,573. It was recognized as early as the 1930's that the amountof hydrochloric acid present in the reaction mixture during partialester hydrolysis must be carefully controlled to avoid hydrolysis orbreakdown of the cellulose acetate. See, for example, U.S. Pat. No.1,878,954.

Likewise, U.S. Pat. No. 2,129,052 advised that hydrolysis under severeconditions such as high temperature or high concentration of catalystcaused degradation of the cellulose, the resulting products beingunsuitable for commercial use because of their low strength. U.S. Pat.No. 2,801,239, relating to the use of zinc chloride as an esterificationcatalyst, cited as an advantage that the process minimized the rate ofbreakdown of the cellulose. U.S. Pat. No. 3,518,249 acknowledged thatlittle interest had been shown in cellulose esters of an extremely lowdegree of polymerization. More recently it was confirmed that the rateof hydrolysis in cellulose esters is controlled by temperature, catalystconcentration, and, to a lesser extent, by the amount of water, and thathigher water content slightly increases the rate of hydrolysis and“helps minimize degradation.” Kirk-Othmer, Encyclopedia of ChemicalTechnology, Fourth Ed., vol. 5, pp. 496-529, 509 (1993), John Wiley &Sons, New York, N.Y.

When used in coating compositions, conventional cellulose esters providemany benefits, including improved hardness, improved aluminum flakeorientation, high clarity, high gloss, decreased dry-to-touch time,improved flow and leveling, improved redissolve resistance, reducedcratering, and reduced blocking. However, the performance properties ofconventional cellulose esters are accompanied by an increase inviscosity, which must be offset by increasing the level of solventsused. With recent concerns of VOC levels in coating compositions, thereremains a need for a cellulose ester product that provides the benefitsof conventional cellulose esters, while providing only a moderateincrease in viscosity without the addition of organic solvents. It wouldclearly be an advance in the art to provide cellulose esters thatprovide the performance properties of conventional cellulose esters,without an undue increase in viscosity when incorporated into coatingcompositions.

Although maintaining the molecular weight of cellulose esters duringesterification and partial hydrolysis has long been deemed important inobtaining a suitable product, there has nonetheless been occasionalmention in the literature of lower molecular weight cellulose esters.

For example, U.S. Pat. No. 3,386,932 discloses a method for reducing themolecular weight of cellulose triacetate with a catalyst such as borontrifluoride, the resulting bifunctional, low molecular weight cellulosetriacetate then being used to produce linear block copolymers. Thisdisclosure emphasizes the importance of maintaining the estersubstitution at the 2-, 3-, and 6-positions of the triacetate, that is,wherein substantially all of the hydroxyl groups of the cellulose havebeen esterified, so that the hydroxyl functionality necessary forformation of the linear block copolymers preferentially appears only onthe ends of the polymer chains.

U.S. Pat. No. 3,391,135 discloses a process in which hydrogen halidesare used to reduce the molecular weight of cellulose derivatives. Theexamples describe methylcellulose powder and methyl-hydroxypropylcellulose reacted with hydrogen chloride to reduce the molecular weight,as evidenced by a reduction in viscosity.

U.S. Pat. No. 3,518,249 describes oligosaccharide tripropionates, havingan average degree of polymerization of from about 4 to about 20 and lowlevels of hydroxyl, that are useful as plasticizers and as controlagents for the manufacture of foamed plastics. The oligosaccharidetripropionates are prepared by degrading a cellulose propionate in thepresence of an acid catalyst. The patentees acknowledge that it has beenan object in the art to provide methods of preventing the degradation ofcellulose esters into low-viscosity oligosaccharide esters.

U.S. Pat. No. 4,532,177 describes base coat compositions that include afilm-forming resin component, selected from alkyd, polyester, acrylicand polyurethane resins, from 1.0 to 15.0% by weight pigment, and from2.0% to 50.0% by weight of a cellulose ester material. The '177 patentsuggests a solution viscosity for the cellulose ester material from0.05-0.005 seconds, an acetyl content from 10.0-15.0% by weight, apropionyl content from 0.1-0.8% by weight, a butyryl content from36.0-40.0% by weight, and a free-hydroxyl content of from 1.0-2.0% byweight. However, the examples of the '177 patent use a cellulose esterhaving a solution viscosity of 0.01, which is approximately equivalentto an inherent viscosity (IV) for such an ester of from about 0.25 toabout 0.30 dL/g, as measured in a 60/40 (wt./wt.) solution ofphenol/tetrachloroethane (PM95) at 25° C. We have found that solutionviscosities less than about 0.01 correlate poorly with IV values and GPCmolecular weight values, although there is a strong correlation betweenIV and GPC molecular weights.

WO 91/16356 describes a process for the preparation of low molecularweight, high-hydroxyl cellulose esters by treating a cellulose polymerwith trifluoroacetic acid, a mineral acid, and an acyl or aryl anhydridein an appropriate carboxylic solvent, followed by optional in situhydrolysis. The cellulose esters obtained according to the disclosureare said to have a number average molecular weight (M_(n)) ranging fromabout 0.01×10⁵ (about 1,000) to about 1.0×10⁵ (about 100,000), and an IV(inherent viscosity) from about 0.2 to about 0.6, as measured at atemperature of 25° C. for a 0.25 gram sample in 100 ml of a 60/40 byweight solution of phenol/tetrachloroethane.

Japanese Kokai Patent Publication No. 51-119089 describes a process forthe preparation of a low molecular weight cellulose mixed organic acidester that involves heating cellulose acetate with a saturated orunsaturated organic acid of 3 or more carbon atoms (propionyl orhigher), in the presence of an acid catalyst, with removal of theresulting acetic acid from the reaction mixture, to obtain a lowermolecular weight cellulose mixed organic acid ester. The startingmaterial for this process is cellulose acetate.

Another patent document naming the same inventors, Japanese Kokai PatentPublication No. 51-119088, discloses a method for the manufacture of alow molecular weight cellulose organic acid ester that includes heatingcellulose acetate with a saturated or unsaturated organic acid at atemperature above 30° C. in the presence of a cation exchange resin, theresulting ester having a lower molecular weight than the startingmaterial. The starting material for the disclosed process is celluloseacetate.

Both of these references teach low molecular weight mixed celluloseesters. The process uses cellulose acetate as starting material, andperforms a transesterification while hydrolyzing the cellulose backbone,the amount of higher mixed ester introduced being relatively low.

U.S. Pat. No. 6,303,670 discloses an ultraviolet-curable cellulosiccoating composition comprising a cellulose acetate, a diepoxy compound,and a photo cationic polymerization catalyst. The cellulose acetateuseful in these compositions is a low molecular weight celluloseacetate, having a number-average molecular weight of from 1,500 to5,000, and is prepared from cellulose triacetate by hydrolysis.According to this disclosure, the degree of substitution of hydroxylgroups must be from 1 to 3, since hydroxyl values of less than 1 aresaid to result in insufficient crosslinking in the final coatingcomposition.

Although efforts have been made to prepare oligosaccharides via stepwiseaddition of anhydroglucose units, these methods are not believed toresult in cellulose derivatives that are suitable for coatingapplications. Further, the costs of such processes would be significant.See, for example, Nishimura, T.; Nakatsubo, F. “Chemical Synthesis ofCellulose Derivatives by a Convergent Synthetic Method and Several ofTheir Properties,” Cellulose, 1997, 4, 109. See also Kawada, T.;Nakatsubo, F.; Umezawa, T.; Murakami, K.; Sakuno, T. “Synthetic Studiesof Cellulose XII: First Chemical Synthesis of Cellooctaose Acetate,”Mokuzai Gakkaishi 1994, 40(7), 738.

The present applicants have unexpectedly discovered that relatively lowmolecular weight cellulose mixed esters, which were thought to lack theproperties necessary to provide the performance characteristics ofconventional molecular weight esters, can be incorporated into coatingcompositions, without an undue increase in viscosity, and without thehigh levels of solvent heretofore necessary in the preparation of highsolids coatings containing cellulose esters. Also surprisingly, theproperties of the resulting coatings, when the coating compositions areapplied and cured, are comparable in most respects to those made usingconventional molecular weight esters.

Various esters according to the invention exhibit improved solubilitiesin a variety of organic solvents, compatibility with various co-resins,and suitable melt stability after prolonged exposure to melttemperatures. Further advantages of the inventive esters are set forthin the following.

SUMMARY OF THE INVENTION

The cellulose mixed esters according to the present invention are low inmolecular weight, have a high maximum degree of substitution (are highlysubstitutable), and provide high solids, low viscosity coatingcompositions, with none of the drawbacks typically associated with lowmolecular weight cellulose esters, such as formation of brittle films.When used as coating additives in combination with one or more resins,the inventive esters do not themselves unduly increase the viscosity ofthe compositions, providing the advantages of conventional celluloseesters without the drawbacks typically associated with their use, suchas an undesirable increase in organic solvent levels to maintain thedesired viscosity.

These new cellulose mixed esters have a high maximum degree ofsubstitution (DS) per anhydroglucose unit on the cellulose backbone inthe fully esterified or partially hydrolyzed form, and generally have aDS for hydroxyl groups of less than about 0.70 (<0.70 DS hydroxyl). Themaximum degree of substitution per anhydroglucose unit for the celluloseesters of this invention is from about 3.08 to about 3.50. These newmixed esters are soluble in a wide range of organic solvents, allowingcoatings formulators a wide latitude of solvent choice. They have aminimal impact on both the solution and spray viscosities of high solidscoatings. These materials exhibit superior compatibility when blendedwith other coating resins, thereby yielding clear films with a widerrange of coatings resins than do conventional cellulose esters.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph plotting log viscosity as a function of concentrationfor solutions of cellulose esters according to the invention andconventional cellulose esters.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to thefollowing detailed description of the invention, and to the Examplesincluded therein.

Before the present compositions of matter and methods are disclosed anddescribed, it is to be understood that this invention is not limited tospecific synthetic methods or to particular formulations, unlessotherwise indicated, and, as such, may vary from the disclosure. It isalso to be understood that the terminology used is for the purpose ofdescribing particular embodiments only, and is not intended to limit thescope of the invention.

The singular forms “a,” “an,” and “the” include plural referents, unlessthe context clearly dictates otherwise.

Optional or optionally means that the subsequently described event orcircumstances may or may not occur. The description includes instanceswhere the event or circumstance occurs, and instances where it does notoccur.

Ranges may be expressed herein as from about one particular value,and/or to about another particular value. When such a range isexpressed, it is to be understood that another embodiment is from theone particular value and/or to the other particular value.

Throughout this application, where patents or publications arereferenced, the disclosures of these references in their entireties areintended to be incorporated by reference into this application, in orderto more fully describe the state of the art to which the inventionpertains.

As used throughout the disclosure, CAB means a cellulose acetatebutyrate; CAP means a cellulose acetate propionate; CA means a celluloseacetate; CMCAB means a carboxymethylcellulose acetate butyrate; CMCAPmeans a carboxymethylcellulose acetate propionate; CMCA means acarboxymethylcellulose acetate; and HS-CAB means an inventive highsolids cellulose acetate butyrate according to the invention, having ahigh maximum degree of substitution, a low degree of polymerization, alow intrinsic viscosity (IV), and a low molecular weight.

Unless indicated otherwise, HS-CAB-55 refers to an inventive high solidscellulose acetate butyrate with a high maximum degree of substitution, alow degree of polymerization, a low IV, a low molecular weight, and ahigh butyryl content (high-butyryl, or from about 52 to about 55 wt. %),prepared along the lines of Example 3, unless noted otherwise; HS-CAB-46refers to an inventive high solids cellulose acetate butyrate with ahigh maximum degree of substitution, a low degree of polymerization, alow IV, a low molecular weight, and a medium to high butyryl content(high mid-butyryl, or from about 43 to about 51 wt. %), prepared alongthe lines of Examples 21-22 unless noted otherwise; HS-CAB-38 refers toan inventive high solids cellulose acetate butyrate with a high maximumdegree of substitution, a low degree of polymerization, a low IV, a lowmolecular weight, and a medium butyryl content (mid-butyryl, or fromabout 35 to about 42 wt. %), prepared along the lines of Example 1,unless noted otherwise; HS-CAB-36 refers to an inventive high solidscellulose acetate butyrate with a high maximum degree of substitution, alow degree of polymerization, a low IV, a low molecular weight, and alow medium butyryl content (low mid-butyryl, or from about 30 to about38 wt. %), prepared along the lines of Example 2, unless notedotherwise; HS-CAB-17 refers to an inventive cellulose acetate butyratewith a high maximum degree of substitution, a low degree ofpolymerization, a low IV, a low molecular weight, and a low butyrylcontent (low-butyryl, or from about 17 to about 24), prepared along thelines of Examples 9-13, unless noted otherwise; HS-CAB-20 likewiserefers to an inventive cellulose acetate butyrate with a high maximumdegree of substitution, a low degree of polymerization, a low IV, a lowmolecular weight, and a low butyryl content (low-butyryl, or from about17 to about 24), prepared along the lines of Examples 9-13, unless notedotherwise, and considered equivalent to an HS-CAB-17, as used throughoutthis application; HS-CAP means an inventive high solids, celluloseacetate propionate with a high maximum degree of substitution, a lowdegree of polymerization, a low IV, and a low molecular weight; andHS-CAP-54 means an inventive high solids, cellulose acetate propionatewith a high maximum degree of substitution, a low degree ofpolymerization, a low IV, and a low molecular weight, and a highpropionyl content (high-propionyl, or from about 49 to about 56 wt. %),prepared along the lines of Example 52, unless noted otherwise.

In one embodiment, the invention relates to cellulose mixed estershaving a total degree of substitution per anhydroglucose unit of fromabout 3.08 to about 3.50, and having the following substitutions: adegree of substitution per anhydroglucose unit of hydroxyl of no morethan about 0.70; a degree of substitution per anhydroglucose unit ofC₃-C₄ esters from about 0.80 to about 1.40, and a degree of substitutionper anhydroglucose unit of acetyl of from about 1.20 to about 2.34.According to this embodiment, the inventive mixed esters exhibit aninherent viscosity from about 0.05 to about 0.15 dL/g, as measured in a60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25° C.; a numberaverage molecular weight (M_(n)) of from about 1,000 to about 5,600; aweight average molecular weight (M_(w)) of from about 1,500 to about10,000; and a polydispersity of from about 1.2 to about 3.5. In variousembodiments, the ester may comprise butyryl, or propionyl, or mixturesof the two.

In various alternative aspects, the degree of substitution peranhydroglucose unit of hydroxyl may be from about 0.05 to about 0.70;the inherent viscosity may be from about 0.05 to about 0.12 dL/g, asmeasured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at25° C.; or the number average molecular weight (M_(n)) may be from about1,500 to about 5,000. In certain embodiments, a preferred polydispersitymay be from 1.2 to 2.5; a preferred inherent viscosity from 0.07 to 0.11dL/g; or a preferred number average molecular weight (M_(n)) from about1,000 to about 4,000. In certain other embodiments, a preferred inherentviscosity may be from about 0.07 to about 0.11 dL/g; or a preferrednumber average molecular weight (M_(n)) from about 1,000 to 4,000.

In a further embodiment, the invention relates to cellulose mixed estershaving a total degree of substitution per anhydroglucose unit of fromabout 3.08 to about 3.50, and having the following substitutions: adegree of substitution per anhydroglucose unit of hydroxyl of no morethan about 0.70; a degree of substitution per anhydroglucose unit ofC₃-C₄ esters from about 1.40 to about 2.45, and a degree of substitutionper anhydroglucose unit of acetyl of from 0.20 to about 0.80. Accordingto this embodiment, the inventive mixed esters exhibit an inherentviscosity of from about 0.05 to about 0.15 dL/g, as measured in a 60/40(wt./wt.) solution of phenol/tetrachloroethane at 25° C.; a numberaverage molecular weight (M_(n)) of from about 1,000 to about 5,600; aweight average molecular weight (M_(w)) of from about 1,500 to about10,000; and a polydispersity of from about 1.2 to about 3.5. In variousembodiments, the ester may comprise butyryl, or propionyl, or mixturesof the two.

In various alternative embodiments, the degree of substitution peranhydroglucose unit of hydroxyl may be from about 0.05 to about 0.70;the inherent viscosity may be from about 0.05 to about 0.12 dL/g, asmeasured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at25° C.; or the number average molecular weight (M_(n)) may be from about1,500 to about 5,000. In certain embodiments, a preferred polydispersitymay be from 1.2 to 2.5; a preferred inherent viscosity from 0.07 to 0.11dL/g; or a preferred number average molecular weight (M_(n)) from about1,000 to about 4,000. In certain other embodiments, a preferred inherentviscosity may be from about 0.07 to about 0.11 dL/g; and a preferrednumber average molecular weight (M_(n)) from about 1,000 to 4,000.

In yet another embodiment, the invention relates to cellulose mixedesters having a total degree of substitution per anhydroglucose unit offrom about 3.08 to about 3.50, and having the following substitutions: adegree of substitution per anhydroglucose unit of hydroxyl of no morethan about 0.70; a degree of substitution per anhydroglucose unit ofC₃-C₄ esters from about 2.11 to about 2.91, and a degree of substitutionper anhydroglucose unit of acetyl of from 0.10 to about 0.50. Accordingto this embodiment, the inventive mixed esters may exhibit an inherentviscosity of from about 0.05 to about 0.15 dL/g, as measured in a 60/40(wt./wt.) solution of phenol/tetrachloroethane at 25° C.; a numberaverage molecular weight (M_(n)) of from about 1,000 to about 5,600; aweight average molecular weight (M_(w)) of from about 1,500 to about10,000; and a polydispersity of from about 1.2 to about 3.5. In variousembodiments, the ester may comprise butyryl, or propionyl, or mixturesof the two.

In various alternative embodiments, the degree of substitution peranhydroglucose unit of hydroxyl may be from about 0.05 to about 0.70;the inherent viscosity may be from about 0.05 to about 0.12 dL/g, asmeasured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at25° C.; or the number average molecular weight (M_(n)) may be from about1,500 to about 5,000. In certain embodiments, a preferred polydispersitymay be from 1.2 to 2.5; a preferred inherent viscosity from 0.07 to 0.11dL/g; and a preferred number average molecular weight (M_(n)) from about1,000 to about 4,000. In certain other embodiments, a preferred inherentviscosity may be from about 0.07 to about 0.11 dL/g; and a preferrednumber average molecular weight (M_(n)) from about 1,000 to 4,000.

The present invention thus provides certain mixed esters of cellulose,which are useful, for example, as binder components and additives incoatings compositions. The inventive esters may have an inherentviscosity of from about 0.05 to about 0.15 dL/g, or from about 0.07 toabout 0.11 dL/g, as measured in a 60/40 (wt./wt.) solution ofphenol/tetrachloroethane at 25° C. (as further defined below), and amaximum degree of substitution per anhydroglucose unit from about 3.08to about 3.50, and a degree of substitution per anhydroglucose unit oforganic esters, for example those having from 1 to 12 carbon atoms,preferably C₂-C₄ alkyl esters, and more preferably saturated C₂-C₄ alkylesters, of about 2.38 to about 3.50. As is described below, these resinsare especially useful in coating and ink formulations. They are solublein a wide range of solvents and solvent blends, as demonstrated in theexamples of this application, making them particularly suited for customcoating formulations. The cellulose esters may be alkyl celluloseesters, such as methylcellulose, or hydroxyalkyl cellulose esters, suchas methyl-hydroxypropyl cellulose esters. However, in some embodiments,the cellulose esters are esters that are not otherwise modified, i.e.the cellulose is modified only by the addition of organic esterfunctionality, not ether functionality or carboxyl functionalityobtained via oxidation chemistry. Certain particular novel esters arepreferred and further provided as additional embodiments of thisinvention.

In yet another embodiment, there is provided a cellulose mixed ester,having a maximum degree of substitution of from about 3.08 to about3.50, a degree of substitution per anhydroglucose unit of hydroxyl fromabout 0.01 up to about 0.70, a degree of substitution per anhydroglucoseunit of C₃-C₄ esters of about 0.8 to about 3.50, a degree ofsubstitution per anhydroglucose unit of acetyl from about 0.05 to about2.00, and having an inherent viscosity of about 0.05 to about 0.15 dL/g,as measured in a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at25° C. In various alternative embodiments, the inherent viscosity may befrom about 0.07 to about 0.11 dL/g, the degree of substitution peranhydroglucose unit of hydroxyl from 0.10 to 0.70, the degree ofsubstitution per anhydroglucose unit of C₃-C₄ esters from 1.10 to 3.25,or the degree of substitution per anhydroglucose unit of acetyl from0.05 to 0.90. Various esters according to this embodiment exhibitsolubility in a wide range of solvents and solvent blends.

In another embodiment, there is provided a cellulose mixed ester, havinga maximum degree of substitution of from about 3.08 to about 3.50, adegree of substitution per anhydroglucose unit of hydroxyl from about0.01 up to about 0.70, a degree of substitution per anhydroglucose unitof C₃-C₄ esters of about 0.8 to about 3.50, a degree of substitution peranhydroglucose unit of acetyl from about 0.05 to about 2.00, and havingan inherent viscosity of about 0.05 to about 0.15 dL/g, as measured in a60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25° C. Invarious alternative embodiments, the inherent viscosity may be fromabout 0.07 to about 0.11 dL/g, the degree of substitution peranhydroglucose unit of hydroxyl about 0, the degree of substitution peranhydroglucose unit of C₃-C₄ esters from 2.60 to 3.40, or the degree ofsubstitution per anhydroglucose unit of acetyl from 0.10 to 0.90.Various esters according to these embodiments exhibit solubility in awide range of solvents and solvent blends.

In another embodiment of the present invention, there is provided acellulose acetate butyrate having a maximum degree of substitution offrom about 3.08 to about 3.50, and a degree of substitution peranhydroglucose unit of hydroxyl from about 0.01 to about 0.70, and adegree of substitution per anhydroglucose unit of butyryl of about 0.80to about 3.44, and a degree of substitution per anhydroglucose unit ofacetyl of about 0.05 to about 2.00, and having an inherent viscosity of0.05 to 0.15 dL/g, as measured in a 60/40 (wt./wt.) solution ofphenol/tetrachloroethane at 25° C. In various alternative embodiments,the inherent viscosity may be from 0.07 to 0.11 dL/g, the degree ofsubstitution per anhydroglucose unit of hydroxyl from 0.10 to 0.70,butyryl from 1.10 to 3.25, or acetyl from 0.10 to 0.90. Various estersaccording to this embodiment exhibit solubility in a wide range ofsolvents and solvent blends.

As a further embodiment, there is provided a cellulose acetatepropionate having a degree of substitution per anhydroglucose unit ofhydroxyl from about 0.01 to about 0.70, and a degree of substitution peranhydroglucose unit of propionyl of about 0.80 to about 3.44 and adegree of substitution per anhydroglucose unit of acetyl of from about0.05 to about 2.00, and having an inherent viscosity of about 0.05 toabout 0.15 dL/g, as measured in a 60/40 (wt./wt.) solution ofphenol/tetrachloroethane at 25° C. In various alternative embodiments,the inherent viscosity may be from 0.07 to 0.11 dL/g, the degree ofsubstitution per anhydroglucose unit of hydroxyl from 0.10 to 0.70, thedegree of substitution per anhydroglucose unit of propionyl from 1.10 to3.25, or the degree of substitution per anhydroglucose unit of acetyl offrom 0.10 to 0.90. Various esters according to this embodiment exhibitsolubility in a wide range of solvents and solvent blends.

Different grades and sources of cellulose are available and are usefulaccording to the invention, and can be selected from cotton linters,softwood pulp, hardwood pulp, corn fiber and other agricultural sources,and bacterial cellulose, among others. The source of cellulose used toprepare the cellulose esters of the invention is important in providinga product having suitable properties. It is generally preferred that adissolving-grade cellulose be used as starting material for preparingthe cellulose esters of this invention. It is more preferred that thedissolving-grade cellulose have an α-cellulose content of greater than94%. Those skilled in the art will also recognize that the use ofcellulose from different sources may require modifications to thereaction conditions (e.g. temperature, catalyst loading, time) in orderto account for any differences in the reactivity of the cellulose.

In certain embodiments, it is preferred that the source of cellulose bea natural cellulose as just described, and that the source of cellulosenot be a modified cellulose such as a cellulose ether, e.g. an alkylcellulose. Similarly, in certain embodiments, it is preferred that thecellulose starting material not be a carboxyalkylcellulose, such ascarboxymethylcellulose, or any cellulose derivative having acidfunctionality. These cellulose derivatives are more expensive than thenaturally-derived cellulose just described, and in many cases result inesters that are less suitable than the inventive esters in coatingformulations, especially those containing appreciable amounts of organicsolvents. It also follows that certain of the inventive esters accordingto the invention have an acid value no greater than about 5, or nogreater than about 1. Suitable cellulose esters containing carboxylfunctionality are being separately pursued in a copending applicationfiled herewith.

The cellulose esters of the invention may be prepared by a multi-stepprocess. In this process, cellulose is water-activated, followed bywater displacement via solvent exchange with an alkanoic acid such asacetic acid, followed by treatment with a higher alkanoic acid(propionic acid or butyric acid) to give a cellulose activate wet withthe appropriate alkanoic acid. Next, the cellulose activate is treatedwith the desired anhydride, in the presence of a strong acid catalystsuch as sulfuric acid, to give essentially a fully-substituted celluloseester having a lower molecular weight than conventional esters. Asolution consisting of water and an alkanoic acid is added slowly to theanhydrous “dope” solution so as to allow removal of combined sulfur fromthe cellulose backbone. The final addition allows a slow transitionthrough the hydrous point to give a period of low water concentrationand high temperature (as a result of the exotherm from water reactingwith excess anhydride) in the reaction medium. This is important forhydrolysis of combined sulfur from the cellulose backbone. This productis then hydrolyzed using sulfuric acid to provide a partiallysubstituted cellulose ester. Hydrolysis is important to provide gel-freesolutions in organic solvents, and to provide better compatibility withother resins in coatings applications. The hydroxyl groups exposedduring hydrolysis are also important crosslinking sites in many coatingsapplications.

Next, the sulfuric acid is neutralized after the esterification orhydrolysis reactions are complete by addition of a stoichiometric amountof an alkali or alkaline earth metal alkanoate, for example, magnesiumacetate, dissolved in water and an alkanoic acid such as acetic acid.Neutralization of the strong acid catalyst is important for optimalthermal and hydrolytic stability of the final product.

Finally, either the fully substituted or partially hydrolyzed forms ofcellulose ester are isolated by diluting the final neutralized “dope”with an equal volume of acetic acid followed by precipitation of thediluted “dope” into a volume of water about 20 to 30 times its weight,to give a particle that can be easily washed with deionized water toefficiently remove residual organic acids and inorganic salts. In manycases, a fairly sticky precipitate is initially formed. The precipitatecan be hardened by exchanging the precipitation liquid for fresh waterand allowing the precipitate to stand. The hardened precipitate can thenbe easily washed and ground up as necessary.

The key descriptors of the composition of a cellulose ester are thelevel of substitution of the various ester groups (i.e. degree ofsubstitution or wt. % are commonly used and are discussed in detail inother parts of this application), the level of hydroxyl groups, and thesize of the polymer backbone, which can be inferred from IV, viscosity,and GPC data. The key factors that influence the resulting compositionof the inventive cellulose mixed esters thus produced are: aceticanhydride level, acetic acid level, butyric (or propionic) anhydridelevel, butyric (or propionic) acid level, water level, cellulose level,catalyst type, catalyst level, time, and temperature. One skilled in theart will appreciate that higher catalyst loadings, higher temperatures,and/or longer reaction times during esterification are used to producethe inventive cellulose esters, having lower molecular weights thanconventional esters.

Thus, as a further aspect of the invention, the cellulose esters of theinvention may be prepared by a multi-step process. In the processaccording to the invention, cellulose is water-activated, followed bywater displacement via solvent exchange with an alkanoic acid such asacetic acid, followed by solvent exchange with a higher alkanoic acid(e.g. propionic acid or butyric acid) to give a cellulose-activate wetwith the appropriate alkanoic acid (e.g. propionic or butyric acid). Inthis regard, we have found that it is important that the startingcellulose has a 94 to 99% alpha content, preferably about 95 to 98%alpha cellulose content. The high alpha content is important for thequality of the final products prepared therefrom. We have found that lowalpha cellulose pulps lead to poor solubility in organic solvents andconsequently to poor formulations.

Next, the activated cellulose is reacted with the desired anhydride inthe presence of a strong acid catalyst such as sulfuric acid to give afully substituted cellulose ester with a lower molecular weight thanconventional esters. A solution containing water and an alkanoic acid ormixture of alkanoic acids is added slowly to the anhydrous “dope”solution so as to allow removal of combined sulfur from the cellulosebackbone. The final addition allows a slow transition through thehydrous point to give a period of low water concentration and hightemperature (as a result of the exotherm from water reacting with excessanhydride) in the reaction medium. This is important for hydrolysis ofcombined sulfur from the cellulose backbone. This product is thenhydrolyzed using sulfuric acid to provide a partially-substitutedcellulose ester. Hydrolysis is important to provide gel-free solutionsin organic solvents, and to provide better compatibility with otherresins in coatings applications.

Next, the sulfuric acid is neutralized after the esterification orhydrolysis reactions are complete by addition of a stoichiometric amountof an alkali or alkaline earth metal alkanoate, for example magnesiumacetate, dissolved in water and an alkanoic acid such as acetic acid.Neutralization of the strong acid catalyst is important for optimalthermal and hydrolytic stability of the final product.

Finally, either the fully substituted or partially hydrolyzed forms ofcellulose ester are isolated by diluting the final neutralized “dope”with an equal volume of acetic acid followed by precipitation of thediluted “dope” into a volume of water about 20 to 30 times its weight,to give a particle that can be easily washed with deionized water toefficiently remove residual organic acids and inorganic salts. In manycases, a fairly sticky precipitate is initially formed. The precipitatecan be hardened by exchanging the precipitation liquid for fresh waterand allowing the precipitate to stand. The hardened precipitate can thenbe easily washed and ground up as necessary.

In light of the present disclosure, those skilled in the art willreadily appreciate that, of the process parameters just described,higher catalyst loadings, higher temperatures, and/or longer reactiontimes during esterification will be used to obtain the inventivecellulose esters having lower molecular weights than conventionalcellulose esters, as further evidenced in the examples of thisdisclosure.

The cellulose esters according to the invention have a weight averagemolecular weight, M_(w), as measured by GPC, of from about 1,500 toabout 10,000; or from about 2,000 to about 8,500; a number averagemolecular weight, M_(n), as measured by GPC, of from about 1,500 toabout 6,000; and a polydispersity, defined as M_(w)/M_(n), from about1.2 to about 7, or from about 1.2 to about 3.5, or from about 1.2 toabout 2.5.

The cellulose mixed esters according to the invention, sometimesdescribed herein as HS-CAB's, exhibit compatibility with a wide varietyof co-resins, compatibility being defined as the ability of two or moreresins, when mixed together, to form a stable homogeneous mixture usefulas a coating composition. For example, an HS-CAB with approximately 38wt. % butyryl (sometimes described herein as an HS-CAB-38) exhibitscompatibilities with Eastman's Acrylamac 2328, Akzo Nobel's Microgel,Eastman's Duramac 2314, Bayer's Desmodur 3300, Rhodia's XIDT, andBayer's Desmodur IL, equal to or better than commercialhigher-butyryl-content samples such as CAB-551-0.01 (cellulose acetatebutyrate containing approximately 55 wt. % butyryl, available fromEastman Chemical Company). In some instances, inventive cellulose mixedesters having approximately 38 wt. % butyryl, or approximately 55 wt. %butyryl, are compatible at a 1:1 ester to resin loading with acrylicresins that are not compatible with many conventional molecular weightcellulose esters. Such dramatic shifts in compatibility allowformulators to use a mid-butyryl ester (about 38 wt. %) in applicationsthat might otherwise require a higher butyryl CAB for compatibilitypurposes.

An advantage to being able to use a mid-butyryl ester instead of ahigh-butyryl ester is that when all properties aside from butyryl leveland acetyl level remain constant, i.e. hydroxyl value and molecularweight, the mid-butyryl CAB has a higher T_(g) than its high-butyrylcounterpart. Another advantage to using a mid-butyryl ester over ahigh-butyryl ester is that mid-butyryl commercial esters are often lesssoluble in particular solvents and solvent blends than theirhigh-butyryl counterparts. This same trend is generally observed whencomparing mid-butyryl HS-CAB's with high-butyryl HS-CAB's of equivalentmolecular weight and hydroxyl content. Without being bound by theory, webelieve that the observed solubility differences between mid-butyryl andhigh-butyryl esters is responsible in part for the improved redissolveresistance seen with certain of the inventive esters when a topcoat isapplied to a basecoat. We believe that the combination of improvedcompatibility along with improved, but also differentiated, solubilitywill be a valuable asset to coatings formulation chemists.

Thus, conventional cellulose esters with a higher butyryl content tendto be more soluble and have a lower T_(g) than their counterparts havinglower butyryl levels. One result of increased solubility is that theredissolve resistance of the resulting coating is negatively affected.One of the key advantages of a conventional high butyryl cellulose estersuch as CAB-551-0.01 is its increased compatibility with many co-resinswhen compared with a mid-butyryl ester such as CAB-381-0.1. Surprising,we have found that inventive mid-butyryl esters (HS-CAB-38) according tothe invention have better compatibility with co-resins than aconventional molecular weight high butyryl cellulose ester such as aCAB-551-0.01, while exhibiting a similar solubility.

As a result, coatings formulators can use the inventive esters of theinvention in basecoat formulations that cannot tolerate the viscosityincrease imparted by the addition of conventional CAB's, while providingthe redissolve resistance typical of conventional esters having a higherbutyryl content.

As mentioned, the inventive mixed esters likewise demonstratebetter-than-expected redissolve resistance in certain systems. This issurprising, since the inventive mixed esters have a molecular weightlower than conventional cellulose mixed esters. One would instead expectto see a decrease in redissolve resistance with a lowering in molecularweight. As a result, coatings formulators can use the inventive estersof the invention in basecoat formulations that cannot tolerate theviscosity increase imparted by the addition of conventional CAB's, whileproviding the necessary redissolve resistance.

As is also evident from the examples, cellulose esters according to theinvention have excellent melt stability after prolonged exposure to melttemperatures. When HS-CABs according to the invention were used inpreparing pigment grinds on a two-roll mill, no discoloring was observeddue to decomposition even after prolonged exposure (at least 30 minutes)to melt temperatures of about 100° C. to about 120° C. Melt stability isan important property for cellulose esters used in plastic applications,since yellowing, a common result of poor melt stability, is often adetrimental characteristic of cellulosics used in plastics applications.

Further, the inventive esters exhibit a better-defined melting point, asfurther described herein, making them especially suitable for uses wherea well-defined melting point is necessary. Not being bound by theory, weattribute this to a lower polydispersity value than conventional esters.

Traditionally, cellulose esters are considered to have a maximum degreeof substitution of 3.0. A DS of 3.0 indicates that there are 3.0reactive hydroxyl groups in cellulose that can be derivatized. Nativecellulose is a large polysaccharide with a degree of polymerization from700-2,000, and thus the assumption that the maximum DS is 3.0 isapproximately correct. However, as the degree of polymerization islowered, the end groups of the polysaccharide backbone become relativelymore important. In the esters according to the invention, this change inmaximum DS influences the performance of the esters, by changing thesolubility in certain solvents and the compatibility with certaincoatings resins.

Table 1 gives the DS_(Max) at various degrees of polymerization.Mathematically, a degree of polymerization of 401 is required in orderto have a maximum DS of 3.00. As the table indicates, the increase inDS_(Max) that occurs with a decrease in DP is slow, and for the mostpart, assuming a maximum DS of 3.00 is acceptable. However, once the DPis low enough, for example a DP of 21, then it becomes appropriate touse a different maximum DS for all calculations.

TABLE 1 Effect of DSMax on DP DP DS_(Max) 1 5.00 2 4.00 3 3.67 4 3.50 53.40 6 3.33 7 3.29 8 3.25 9 3.22 10 3.20 11 3.18 12 3.17 13 3.15 14 3.1415 3.13 16 3.13 17 3.12 18 3.11 19 3.11 20 3.10 21 3.10 22 3.09 23 3.0924 3.08 25 3.08 50 3.04 75 3.03 100 3.02 134 3.01 401 3.00

The present invention thus provides a cellulose ester with a highmaximum degree of substitution and a low degree of polymerization.

As already described, the inventive esters of the present application,having a high maximum degree of substitution and a low degree ofpolymerization, unexpectedly exhibit rheological performance similar toconventional cellulose esters having a much higher degree ofpolymerization. It is quite surprising that an HS-CAB with such a lowdegree of polymerization would display such rheological performance.

Without being bound by any theory, we believe that the cellulose estersaccording to the invention exhibit a fairly random substitution patternof hydroxyl groups. We believe that this random substitution pattern ofhydroxyl groups is achieved by performing the molecular weight reductionstep prior to hydrolysis of the ester groups. The low molecular weightcellulose ester products of the prior art processes generally exhibit anon-random substitution pattern, particularly at C-4 of the non-reducingterminus and at C-1 (RT1) of the reducing terminus. The products of theprior art generally have a hydroxyl group at C-4 and either a hydroxylor ester at C-1 (RT-1) depending on whether the process is a hydrolysisor an acetolysis reaction.

The widely accepted mechanism presented in Scheme 1 may help the readerto visualize the explanation above. The proposed mechanism presented inScheme 1 depicts the reaction of a polysaccharide with a high degree ofpolymerization, the nature of the groups at C4 and RT1 being influencedby the amount of cleavage that occurs. The substitution at the twocarbons of interest, C4 and RT1, increases to large levels as more andmore glycosidic bonds are cleaved. Scheme 1 shows only a singleglycosidic bond being cleaved and thus only one C4 and one RT1 site havethe substitution pattern displayed by products generated by the priorart. As more and more sites are cleaved, the effect of the substitutionpattern at C4 and RT1 becomes more important.

Processes used to prepare the products of the present invention resultin a fully-esterified cellulose ester having approximately the desireddegree of polymerization while the reaction mixture is still anhydrous(i.e. before hydrolysis). As a result, the hydrolysis of esters duringthe preparation of the products of this invention is believed to produceessentially a random distribution of hydroxyl groups throughout theentire cellulosic backbone. This belief is based, in part, on the uniquesolubility profiles exhibited by the esters according to the invention.Those skilled in the art will recognize that under kineticallycontrolled conditions, hydrolysis will occur preferentially at certainsites (e.g. C6>>C2>C3). The hydrolysis process practiced in thisinvention is performed under thermodynamic control (i.e. underequilibrium conditions), which is believed to result in a more randomdistribution of hydroxyl functionality throughout the cellulosicbackbone.

¹³C-NMR studies suggest that the inventive esters (HS-CAB's) have adifferent substitution pattern than those made by processes in whichmolecular weight is reduced during hydrolysis. The chemical structurebelow highlights the areas where differences in the substitutionpatterns are believed to occur.

Cellulose mixed esters of the invention have utility in pigmentdispersions by blending the cellulose ester and a pigment with heatand/or shear to disperse the pigment. In this manner, pigments can beeasily dispersed in coating formulations and plastics, thereby providinghigh coloring power and good transparency while using a minimal amountof pigment. Such pigment dispersions can be improved by the use of thecellulose esters of the present invention in place of conventionalcellulose esters. As with conventional cellulose esters, the cellulosemixed esters of the present invention impart markedly improved wettingproperties to the pigment dispersion. Mixtures of C₂-C₄ esters ofcellulose and pigments at pigment: ester weight ratios of about 20:80 to50:50 may be prepared. These dispersions can be prepared on a two-rollmill or in a ball mill, Kady mill, sand mill, or the like. The highDS_(Max), low DP cellulose esters of this invention have an advantageover conventional cellulose esters in that they have less of an impacton the viscosity, and thus allow formulations with a higher binder(resin) loading to be used.

Thus, the present invention provides a pigment dispersion comprisingabout 20 to 77 weight percent of a pigment and correspondingly about 33to 80 percent by weight of a C₂-C₄ ester of cellulose having an inherentviscosity of about 0.05 to 0.15 dL/g, as measured in a 60/40 (wt./wt.)solution of phenol/tetrachloroethane at 25° C., and a degree ofsubstitution per anhydroglucose unit of C₂-C₄ esters of about 0.8 toabout 3.5.

The esters of the invention are easily formulated into either lacquer orenamel type coatings where they are used as rheology modifiers and/orbinder components providing improved aluminum flake orientation andimproved hardness. They can provide a water-clear, high gloss,protective coating for a variety of substrates, especially metal andwood.

An additional advantage, when used for example to prepare pigments foruse in plastics or coatings, relates to an increase in melt stabilityexhibited by the esters of the invention. The inventive HS-CABs have asharper melting range than commercial CAB's, possibly due to the tighterpolydispersity of HS-CAB's versus conventional CAB's. HS-CAB's can beblended with a pigment to produce a pigment dispersion. The pigmentdispersions can be prepared by a number of routes including a slurrymethod and by extrusion. The improved melt stability is advantageous inextruder applications, since yellowing of the cellulosic is reduced oreliminated.

Cellulose esters of this invention, especially high DS_(Max), low DPcellulose acetate butyrate and high DS_(Max), low DP cellulose acetatepropionate, as described above, exhibit improved solubility andcompatibility (i.e., film clarity) characteristics over manyconventional cellulose esters (cellulose acetate, cellulose propionate,cellulose butyrate, cellulose acetate propionate, or cellulose acetatebutyrate).

For example, conventional mid-butyryl cellulose esters such asCAB-381-0.1 (available from Eastman Chemical Company, Kingsport, Tenn.),as evidenced for example in Comparative Example 31 and Example 49, arenot readily soluble in Eastman C-11 ketone (a mixture of saturated andunsaturated, linear and cyclic ketones), Eastman DIBK (diisobutylketone), PP (propylene glycol monopropyl ether), Eastman EP solvent(ethylene glycol monopropyl ether), Eastman EB solvent (ethylene glycolmonobutyl ether), methanol, Tecsol C solvent, 95% (ethanol withmethanol, methyl isobutyl ketone, and ethyl acetate as denaturants with5% water), toluene, or a 90/10 isopropyl alcohol/water blend. Incontrast, certain inventive esters such as certain of the HS-CAB-38s (asexemplified in Example 28 and Example 49) of the invention are solublein each of the solvents or solvent systems described above. By the term“soluble,” as used throughout the specification, we mean that a clearsolution is obtained when a 10% (wt/wt) mixture of the cellulose esterin the desired solvent is prepared, unless stated otherwise.

As another example, conventional high-butyryl cellulose esters such asCAB-551-0.01 (available from Eastman Chemical Company), as evidenced inComparative Example 32 and Example 49, are not readily soluble inmethanol, Tecsol C solvent, 95%, toluene (the ester gels), or a 90/10isopropyl alcohol/water blend. In contrast, certain inventive esters,such as certain of the high-butyryl cellulose esters (HS-CAB-55's), asevidenced in Example 29 and some of the inventive esters of Example 49,are soluble in each of the solvents or solvent systems described above.

Similarly, conventional low-butyryl cellulose esters such as CAB-171-15S(available from Eastman Chemical Company), as evidenced in ComparativeExample 33, are not readily soluble in Eastman PM solvent (propyleneglycol monomethyl ether), and only partially soluble in Eastman PMacetate (propylene glycol methyl acetate) and Eastman DM solvent(diethylene glycol methyl ether). In contrast, certain inventive esters,such as certain of the low-butyryl cellulose esters HS-CAB-17s andHS-CAB-20s, as evidenced in Example 30 and Example 49, are soluble ineach of these solvents or solvent systems.

It is important to recognize that, as with conventional molecular weightesters, there are important factors other than butyryl content thatinfluence the solubility of HS-CAB's, such as acetyl/butyryl ratio andhydroxyl content. This can be seen especially in Example 49, in whichvarying levels of hydroxyl and acetate affect the solubility of estershaving similar butyryl content. These ester substitutions may be variedby those skilled in the art, in light of the present disclosure, toobtain the desired solubility in a given solvent, and the desiredcompatibility with a given resin. We note that the inventive estersevidence increased solubility, when compared with those esters havingconventional molecular weight, at similar hydroxyl and acetate levels.

As demonstrated in the examples, the inventive esters are soluble inmost classes of typical coating solvents, including ketones, esters,alcohols, glycol ethers, and glycol ether esters, while toleratingdilution with water or aromatic hydrocarbons.

Examples of typical solvents in which the inventive esters exhibitsolubility include acetone, methyl ethyl ketone, methyl isobutyl ketone,methyl amyl ketone, methyl propyl ketone, 2-propoxyethanol,2-butoxyethanol, ethyl 3-ethoxypropionate, ethanol, methanol isopropylalcohol, diacetone alcohol, ethylene glycol monobutyl ether acetate,ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate,isobutyl acetate diethylene glycol ethyl ether, Eastman PM acetate(propylene glycol methyl acetate), Eastman EB acetate (ethylene glycolbutyl acetate), Eastman PM Solvent (propylene glycol monomethyl ether),Eastman DM Solvent (diethylene glycol methyl ether), Eastman PB Solvent(propylene glycol monobutyl ether, Eastman DE Solvent (diethylene glycolethyl ether), Eastman PP Solvent (propylene glycol monopropyl ether),Eastman EP Solvent (ethylene glycol monopropyl ether), Eastman EBSolvent (ethylene glycol monobutyl ether), Eastman 95% Tecsol C (ethanolwith methanol, MIBK and ethyl acetate as denaturants with 5% water),N-methylpyrrolidone, Eastman EEP Solvent (ethyl 3-ethoxypropionate), andother volatile inert solvents typically used in coating compositions.For example, organic solutions of the esters of this invention can beprepared by adding 1 to 1000 parts of solvent per part of ester; 1.5 to9 parts of solvent per part of ester is preferred.

The esters of the present invention exhibit viscosities in organicsolutions that in many cases differ substantially from those ofconventional molecular weight esters. Thus, in Example 34 of the presentdisclosure, the viscosities of an HS-CAB-38 (Sample 4, Table 4) and anHS-CAB-55 (Sample 5, Table 4) are compared to the lowest viscositycommercial cellulose esters, CAB-381-0.1 and CAB-551-0.01, of comparablebutyryl content, using as solvent a 90/10 by weight mixture of n-butylacetate/xylene. FIG. 1 shows a representative comparison of the relativeviscosity at each measured concentration. The log viscosities vs.concentration plots are parallel for each of the esters, indicating thateach of the esters has a similar exponential viscosity rise withconcentration, except that the lower the molecular weight of the ester,the higher the concentration becomes to display the same behavior.Additional Brookfield viscosity data are presented in Table 6A ofExample 34. Because the inventive esters exhibit a lower viscosity thanconventional esters at the same concentration, they allow coatingformulations having a higher ester content at the target viscosity.

Thus, some conventional high-butyryl cellulose esters such asCAB-551-0.01 (available from Eastman Chemical Company), as evidenced inTable 6A of Example 34, exhibit a viscosity greater than 10,000centipoise (in a 90/10 by weight mixture of n-butyl acetate/xylene) as a50 wt. % solution. In contrast, certain inventive esters havingcomparable butyryl content (HS-CAB-55) exhibit viscosities in the samesolution of less than 200 centipoise at a 50 wt. % solution.

Likewise, conventional mid-butyryl cellulose esters such as CAB-381-0.1(available from Eastman Chemical Company, Kingsport, Tenn.), asevidenced in Example 34, exhibit a viscosity greater than 500,000centipoise (in a 90/10 by weight mixture of n-butyl acetate/xylene) as a50 wt. % solution. In contrast, certain inventive esters havingcomparable butyryl content (HS-CAB-38) exhibit viscosities in the samesolution of less than 500 centipoise at a 50 wt. % solution.

Further, certain inventive low-butyryl cellulose esters such asHS-CAB-17, as can be seen in Table 6A of Example 34, exhibit viscositiesno greater than 6,000 centipoise, and others no greater than 3,000centipose, as a 50 wt. % solution in a 90/10 by weight mixture ofn-butyl acetate/xylene.

Further, the esters of the present invention are relatively hardpolymers, i.e., about 12 Knoop Hardness Units (KHU), and have high glasstransition temperatures. They can be added to other resins to improvethe coating hardness, and to improve properties such as slip, sagresistance, and mar resistance. To further improve the toughness,crosslinkers such as melamines or isocyanates may be added to react withthese esters or with other resins.

The esters of the present invention may possess free hydroxyl groups,and thus may be utilized in conjunction with crosslinking agents such asmelamines and isocyanates. Such melamines are preferably compoundshaving a plurality of —N(CH₂OR)₂ functional groups, wherein R is C₁-C₄alkyl, preferably methyl. In general, the melamine cross-linking agentmay be selected from compounds of the following formula, wherein R isindependently C₁-C₄ alkyl:

In this regard, preferred cross-linking agents includehexamethoxymethylamine, tetramethoxymethylbenzo-guanamine,tetramethoxymethylurea, mixed butoxy/methoxy substituted melamines, andthe like. The most preferred melamine cross-linking agent ishexamethoxymethylamine.

Typical isocyanate crosslinking agents and resins include hexamethylenediisocyanate (HMDI), isophorone diisocyanate (IPDI), and toluenediisocyanate.

The cellulose esters of this invention are effective flow additives forhigh solids coatings formulations. Addition of the cellulose estersaccording to the invention to high solids coatings formulationsgenerally results in the elimination of surface defects in the film uponcuring/drying (i.e. elimination of pinholing and orange peel). Adistinct advantage that high DS_(Max), low DP cellulose esters have overconventional cellulose esters is that the inventive esters have aminimal impact on solution and/or spray viscosity when added to highsolids coatings formulations. The percent solids can be increased, thusreducing the VOC of the formulation. Conventional cellulose esters canbe used in these same applications as flow additives, but a reduction insolids must generally accompany the addition of the conventionalcellulose esters. That is, the solvent level must be increased so as tomaintain a desirable viscosity.

The invention therefore relates also to coating compositions containingthe cellulose mixed esters according to the invention.

Thus, the present invention provides a coating composition comprising

(a) about 0.1 to about 50 weight percent, based on the total weight (a)and (b) in said composition, of a C₂-C₄ mixed ester of cellulose, withan inherent viscosity of about 0.05 to 0.15 dL/g, as measured in a 60/40(wt./wt.) solution of phenol/tetrachloroethane at 25° C., and a degreeof substitution per anhydroglucose unit of C₂-C₄ esters of about 1.5 toabout 3.50;(b) about 0.1 to 92 weight percent, based on the total weight of (a) and(b) in said composition, of a resin selected from the group consistingof polyesters, polyester-amides, cellulose esters, alkyds,polyurethanes, epoxy resins, polyamides, acrylics, vinyl polymers,polyisocyanates, melamines, phenolics, urea resins, urethane resins, andpolyamides; and(c) a solvent, preferably an organic solvent, or a solvent mixture;wherein the total weight of (a) and (b) is about 5 to 95 weight percentof the total weight of (a), (b), and (c).

In the compositions of the invention, the total weight of (a), (b), and(c) will of course equal 100%.

It is recognized that additional additives can be used in the previouslydescribed compositions, including the following: flow additives,leveling additives, wetting and dispering agents, defoamers, adhesionpromoters, slip aids, anti-skinning agents, UV stabilizers, biocides,mildewcides, fungicides, pigments, and others.

The mixed cellulose esters of the present invention may also be utilizedin waterborne coating compositions. For example, the inventive estersmay be dissolved in organic solvents, treated with either an amine or asurfactant, and dispersed in water. Examples of such solvents include,but are not limited to, 2-butanone, methyl amyl ketone, methanol,ethanol, ethyl 3-ethoxypropionate, ethylene glycol monoethyl ether,ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether,and the like. Dispersion of the cellulose esters of the presentinvention in water is facilitated by addition of an amine or asurfactant. Typical amines include, but are not limited to, ammonia,piperidine, 4-ethylmorpholine, diethanolamine, triethanolamine,ethanolamine, tributylamine, dibutylamine, and dimethylamino ethanol.Surfactants include but are not limited to Aerosol OT, as well as othersurfactants known in the art, such as those set out below.

Examples of dispersing agents and surfactants include sodiumbis(tridecyl) sulfosuccinate, di(2-ethyl hexyl) sodium sulfosuccinate,sodium dihexylsulfosuccinate, sodium dicyclohexyl sulfosuccinate, diamylsodium sulfosuccinate, sodium diisobutyl sulfosuccinate, disodiumiso-decyl sulfosuccinate, disodium ethoxylated alcohol half ester ofsulfosuccinic acid, disodium alkyl amido polyethoxy sulfosuccinate,tetrasodium N-(1,2-dicarboxy-ethyl)-N-oxtadecyl sulfosuccinamate,disodium N-octasulfosuccinamate, sulfated ethoxylated nonylphenol,2-amino-2-methyl-1-propanol, and the like.

Alternatively, the inventive cellulose esters may be combined with oneor more co-resins to assist dispersion. The amount of suitable aqueoussolvent in the dispersed coating composition of such embodiments may befrom about 50 to about 90 wt %, or from about 75 to about 90 wt %, ofthe total coating composition.

Thus, as a further aspect of the present invention, there is provided awaterborne coating composition comprising:

-   -   (a) about 0.1 to about 50 weight percent, based on the total        weight of (a) and (b), of a C₂-C₄ ester of cellulose, exhibiting        an inherent viscosity of about 0.05 to 0.15 dL/g, as measured in        a 60/40 (wt./wt.) solution of phenol/tetrachloroethane at 25°        C., and having substitutions as defined elsewhere herein,        wherein the C₂-C₄ ester has been partially neutralized with        ammonia or an amine;    -   (b) at least 50 weight percent, based on the total weight of (a)        and (b), of a compatible water soluble or water dispersible        resin selected from the group consisting of polyesters,        polyesteramides, cellulose esters, alkyds, polyurethanes, epoxy        resins, polyamides, acrylics, vinyl polymers, polyurethanes, and        melamines;    -   (c) water; and    -   (d) an organic solvent;        wherein the total weight of (a) and (b) is between 5 and 50        weight percent of the total composition and the organic solvent        comprises less than 20 weight percent of the total weight of the        composition.

As a further aspect of the present invention, the above compositions arefurther comprised of one or more coatings additives. Such additives aregenerally present in a range of about 0.1 to 15 weight percent, based onthe total weight of the composition. Examples of such coatings additivesinclude leveling, rheology, and flow control agents such as silicones,fluorocarbons or cellulosics; flatting agents; pigment wetting anddispersing agents; surfactants; ultraviolet (UV) absorbers; UV lightstabilizers; tinting pigments; defoaming and antifoaming agents;anti-settling, anti-sag and bodying agents; anti-skinning agents;anti-flooding and anti-floating agents; fungicides and mildewcides;corrosion inhibitors; thickening agents; or coalescing agents.

Specific examples of additional coatings additives can be found in RawMaterials Index, published by the National Paint & Coatings Association,1500 Rhode Island Avenue, N.W., Washington, D.C. 20005.

Examples of flatting agents include synthetic silica, available from theDavison Chemical Division of W. R. Grace & Company under the trademarkSYLOID™; polypropylene, available from Hercules Inc., under thetrademark HERCOFLAT™; synthetic silicate, available from J. M HuberCorporation under the trademark ZEOLEX™; and polyethylene.

Examples of dispersing agents and surfactants include sodiumbis(tridecyl) sulfosuccinate, di(2-ethylhexyl) sodium sulfosuccinate,sodium dihexylsulfosuccinate, sodium dicyclohexyl sulfosuccinate, diamylsodium sulfosuccinate, sodium diisobutyl sulfosuccinate, disodiumisodecyl sulfosuccinate, disodium ethoxylated alcohol half ester ofsulfosuccinic acid, disodium alkyl amido polyethoxy sulfosuccinate,tetrasodium N-(1,2-dicarboxy-ethyl)-N-oxtadecyl sulfosuccinamate,disodium N-octasulfosuccinamate, sulfated ethoxylated nonylphenol,2-amino-2-methyl-1-propanol, and the like.

Examples of viscosity, suspension, and flow control agents includepolyaminoamide phosphate, high molecular weight carboxylic acid salts ofpolyamine amides, and alkyl amine salt of an unsaturated fatty acid, allare available from BYK Chemie U.S.A. under the trademark ANTI TERRA™.Further examples include polysiloxane copolymers, polyacrylate solution,cellulose esters, hydroxyethyl cellulose, hydrophobically modifiedhydroxyethyl cellulose, hydroxypropyl cellulose, polyamide wax,polyolefin wax, carboxymethyl cellulose, ammonium polyacrylate, sodiumpolyacrylate, and polyethylene oxide.

Several proprietary antifoaming agents are commercially available, forexample, under the trademark BRUBREAK of Buckman Laboratories Inc.,under the BYK™ trademark of BYK Chemie, U.S.A., under the FOAMASTER™ andNOPCO™ trademarks of Henkel Corp./Coating Chemicals, under the DREWPLUS™trademark of the Drew Industrial Division of Ashland Chemical Company,under the TROYSOL™ and TROYKYD™ trademarks of Troy Chemical Corporation,and under the SAG™ trademark of Union Carbide Corporation.

Examples of fungicides, mildewcides, and biocides include4,4-dimethyloxazolidine, 3,4,4-trimethyl-oxazolidine, modified bariummetaborate, potassium N-hydroxy-methyl-N-methyldithiocarbamate,2-(thiocyano-methylthio) benzothiazole, potassium dimethyldithiocarbamate, adamantane, N-(trichloromethylthio) phthalimide,2,4,5,6-tetrachloroisophthalonitrile, orthophenyl phenol,2,4,5-trichlorophenol, dehydroacetic acid, copper naphthenate, copperoctoate, organic arsenic, tributyl tin oxide, zinc naphthenate, andcopper 8-quinolinate.

Examples of U.V. absorbers and U.V. light stabilizers includesubstituted benzophenone, substituted benzotriazole, hindered amine, andhindered benzoate, available from American Cyanamide Company under thetrade name Cyasorb UV, and available from Ciba Geigy under the trademarkTINUVIN, and diethyl-3-acetyl-4-hydroxy-benzyl-phosphonate,4-dodecyloxy-2-hydroxy benzophenone, and resorcinol monobenzoate.

To prepare coated articles according to the present invention, aformulated coating composition containing the cellulose esters of thepresent invention is applied to a substrate and allowed to dry. Thesubstrate can be, for example, wood; plastic; metal, such as aluminum orsteel; cardboard; glass; cellulose acetate butyrate sheeting; andvarious blends containing, for example, polypropylene, polycarbonate,polyesters such as polyethylene terephthalate, acrylic sheeting, as wellas other solid substrates.

Pigments suitable for use in the coating compositions according to thepresent invention are the typical organic and inorganic pigments,well-known to one of ordinary skill in the art of surface coatings,especially those set forth by the Colour Index, 3d Ed., 2d Rev., 1982,published by the Society of Dyers and Colourists in association with theAmerican Association of Textile Chemists and Colorists. Examplesinclude, but are not limited to the following: CI Pigment White 6(titanium dioxide); CI Pigment Red 101 (red iron oxide); CI PigmentYellow 42, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 (copperphthalocyanines); CI Pigment Red 49:1; and CI Pigment Red 57:1.

The conventional cellulose acetate butyrates described in this inventionwere commercial samples from Eastman Chemical Company, Kingsport, Tenn.,as follows: CAB-171-15, CAB-381-0.1, CAB-381-0.5, CAB-381-20,CAB-551-0.01 and CAB-551-0.2. Commercial CMCAB samples were from EastmanChemical Company as follows: CMCAB-641-0.5 and CMCAB-641-0.2.

The following commercial coating resins, representative of those used incoatings, were used to demonstrate the compatibility of the inventiveesters with a wide variety of coatings resins: Desmodur HL was obtainedfrom Bayer as a 60% solution in butyl acetate. Eastman's Polymac HS220-2010 (polyester), Eastman's Duramac HS 2706 (alkyd resin), Eastman'sPolymac HS 5776 (polyester), Eastman's Acrylamac 232-1700 (acrylicresin), Versamid 750 (polyamide), UCAR's VYHD (polyvinylchloride/acetate), Eastman's Duramac 207-2706 (TOFA short oil alkydresin), Eastman's Duramac 5205 (coconut medium oil alkyd resin), Cytec'sCymel 303 (HMM melamine), Cytec's Beetle 65 (urea-formaldehyde), Bayer'sDes N 3300 (polyisocyante), DuPont's Epon 1001F (epoxy resin), Bayer'sDesmodur N 75 BA (aliphatic polyisocyanate), Actichem's Synocure 851 S(acrylic resin), Rohm & Haas Acryloid AT954 (acrylic resin), R&HAcryloid B-44 (acrylic resin), R&H Paraloid A-21 (acrylic lacquer),DuPont ELVACITE 2008 (acrylic lacquer), Polymac HS220-2010 (polyester),Cytec's BEETLE 65 (urea formaldehyde), UC CK-2103 (phenolic), Rohm &Haas Paraloid WR97 (acrylic lacquer, R&H Acryloid AU608X (acrylicresin), VERSAMID 750 (polyamide), Eastman's Duramac 207-2706 (alkydresin), Eastman's Duramac 5205 (alkyd resin), Duramac 51-5135 (alkydresin), Duramac 207-1405 (alkyd resin), DuPont's ELVACITE 2044 (ethylmethacrylate), Bayer's Des N 3300 (polymeric isocyanate), EastmanReactol 175 (acrylic polyol), Akzo Nobel Microgel (thermoset acrylic),Eastman Duramac 1205 (alkyd resin), Eastman Duramac 2706 (alkyd resin),Eastman Duramac 2314 (alkyd resin), Resimene CE-7103 (melamine),Resimene 755 (melamine), Desmophen 1800 (polyester), Bayer Desmodur 3300(isocyanate), Shell Epon 1001F (epoxy), Dow DER 542 (epoxy), Rhodia XIDT(isocyanate), Bayer Desmodur IL (isocyanate), Eastman Carbamac HS4372(polyurethane), UCC UCAR VYHD (vinyl chloride/vinyl acetate), UCAR VMCH(vinyl chloride/vinyl acetate), DuPont LVAX 40 (Vinyl chloride/vinylacetate), and Henkle Verasmid 750 (Polyamide).

In the present disclosure, the following terms have the given meanings:

Strike-in means redissolve of the basecoat caused by the solvents in aclearcoat and typically results in a mottled or muddy appearance of thebasecoat pigment/metal flakes.

High Solids Coatings are coatings with a higher % solids in theformulation than traditional coatings, this typically means coatingsformulations with a % solids level greater than or equal to 60%.

Medium Solids Coatings are coatings with a higher % solids in theformulation than low solids coatings, this typically means coatingsformulations with a % solids level between 40% and 60%.

Low Solids Coatings are coatings with a low % solids in the formulation,this typically means coatings formulations with a % solids level lessthan 40%.

Gloss is a subjective term used to describe the relative amount andnature of mirror like reflection.

Orange Peel is a paint surface appearance resembling an orange skintexture.

A Surface Defect is any abnormality on the surface of a coating thatadversely affects the appearance of the coating; examples includepinholes, craters, and orange peel.

Pinholes (Pinholing) are film surface defects characterized by smallpore-like flaws in a coating, which extend entirely through the coatingand have the general appearance of pinpricks.

Craters are small bowl-shaped depressions frequently having drops orbands of material at their centers and raised circular edges in acoating film.

Cratering is the formation in a wet coating film of small bowl-shapeddepressions that persist after drying.

Dry-To-Touch Time is the interval between application and tack-free time(i.e. the amount of time required for a coating to feel dry.

Reducing Terminus means the terminal saccharide of a disaccharide,trisaccharide, oligosaccharide or polysaccharide that has no othersaccharide attached at C1. The C1 can be functionalized with either ahydroxyl group or an ester group.

Non-reducing Terminus means the terminal saccharide of a disaccharide,trisaccharide, oligosaccharide or polysaccharide that has no othersaccharide attached at C4. The C4 can be functionalized with either ahydroxyl group or an ester group.

Acetolysis means the cleavage of a glycosidic bond in the absence ofwater and in the presence of a catalyst and a carboxylic acid, includingbut not limited to acetic acid.

Hydrolysis means the cleavage of a glycosidic bond in the presence ofwater and a catalyst.

Hydrolysis also means the cleavage of an ester linkage of a celluloseester in the presence of water and a catalyst to generate a freehydroxyl group on the cellulosic backbone.

Travel means change in color as the angle of viewing a goniochromaticmaterial, such as a metallic paint film, is changed from theperpendicular to near-grazing. Sometimes called flop or flip-flop.

Flop means where two different painted panels appear to be a good matchfor color when viewed at a given angle, but appear different at allother angles.

Double Rub is the act of rubbing a solvent saturated cloth in onecomplete forward and backward motion over the coated surface.

Mandrel Bends is a test for determining the flexibility and adhesion ofsurface coatings, so named because it involves the bending of coatedmetal panels around mandrels. [adapted from ASTM procedure D-522]

Certain of the definitions were adapted from Coatings EncyclopedicDictionary, ed. LeSota, S.; 1995, Federation of Societies for CoatingsTechnology, Blue Bell, Pa., incorporated herein by reference.

As used in the examples and throughout the application, MEK means methylethyl ketone; MPK means methyl propyl ketone; MAK means methyl amylketone; PM acetate or Eastman PM acetate means propylene glycol methylacetate; EB acetate or Eastman EB acetate means ethylene glycol butylacetate; PM or Eastman PM means propylene glycol monomethyl ether; DM orEastman DM means diethylene glycol methyl ether; PB or Eastman PB meanspropylene glycol monobutyl ether; DE or Eastman DE means diethyleneglycol ethyl ether; PP or Eastman PP means propylene glycol monopropylether; EP Solvent or Eastman EP Solvent means ethylene glycol monopropylether; EB Solvent or Eastman EB Solvent means ethylene glycol monobutylether; Tecsol C, 95% means ethanol with methanol, MIBK and ethyl acetateas denaturants with 5% water; NMP means n-methyl pyrrolidone; and EEPSolvent or Eastman EEP Solvent means ethyl 3-ethoxypropionate.

EXPERIMENTAL

The ¹H NMR results are obtained using a JEOL Model GX-400 NMRspectrometer operated at 400 MHz. Sample tube size is 5 mm. The sampletemperature is 80° C., the pulse delay 5 sec. and 64 scans are acquiredfor each experiment. Chemical shifts are reported in ppm fromtetramethylsilane, with residual DMSO as an internal reference. Thechemical shift of residual DMSO is set to 2.49 ppm.

For any carboxy(C₁-C₃)alkylcellulose esters, a GC method is used todetermine acetyl, propionyl, and butyryl, rather than NMR, because themethylene of the carboxyl(C₁-C₃)alkyl group cannot be separated from thering protons of the cellulose backbone, making absolute DS measurementsby NMR difficult. The DS values are calculated by converting the acidnumber to percent carboxymethyl and using this along with the GC weightpercents of acetyl, propionyl, and butyryl.

The acetyl, propionyl, and butyryl weight percents are determined by ahydrolysis GC method. In this method, about 1 g of ester is weighed intoa weighing bottle and dried in a vacuum oven at 105° C. for at least 30minutes. Then 0.500±0.001 g of sample is weighed into a 250 mLErlenmeyer flask. To this flask is added 50 mL of a solution of 9.16 gisovaleric acid, 99%, in 2000 mL pyridine. This mixture is heated toreflux for about 10 minutes, after which 30 mL of isopropanolicpotassium hydroxide solution is added. This mixture is heated at refluxfor about 10 minutes. The mixture is allowed to cool with stirring for20 minutes, and then 3 mL of concentrated hydrochloric acid is added.The mixture is stirred for 5 minutes, and then allowed to settle for 5minutes. About 3 mL of solution is transferred to a centrifuge tube andcentrifuged for about 5 minutes. The liquid is analyzed by GC (splitinjection and flame ionization detector) with a 25M X 0.53 mm fusedsilica column with 1 μm FFAP phase.

The weight percent acyl is calculated as follows, where:

C_(i)=concentration of I (acyl group)

F_(i)=relative response factor for component I

F_(s)=relative response factor for isovaleric acid

A_(i)=area of component I

A_(s)=area of isovaleric acid

R=(grams of isovaleric acid)/(g sample)C _(i)=((F _(i) *A _(i))/F _(s) *A _(s)))*R*100

This GC method is used, along with NMR, to determine weight % acetyl,propionyl, and butyryl, and the method used is indicated.

We note that wt. % substitutions may be converted to degree ofsubstitution (DS) values, according to the following:

Wt. % Butyryl is calculated using the following equation:Wt. %Bu=(DS_(Bu)*MW_(Bu))/((DS_(Ac)*MW_(AcKet))+(DS_(Bu)*MW_(BuKet))+MW_(anhydroglu))

Wt. % Acetyl is calculated using the following equation:Wt. %Ac=(DS_(Ac)*MW_(Ac))/((DS_(Ac)*MW_(AcKet))+(DS_(Bu)*MW_(BuKet))+MW_(anhydroglu))

Wt. % Hydroxyl is calculated using the following equation:Wt. %OH=(DS_(Max)−DS_(Ac)−DS_(Bu))*MW_(OH)/((DS_(Ac)*MW_(AcKet))+(DS_(Bu)*MW_(BuKet))+MW_(anhydroglu))

Unless otherwise noted:

DS_(Ac)=Degree of substitution of butyryl as determined by ¹H-NMR

DS_(Bu)=Degree of substitution of butyryl as determined by ¹H-NMR

MW_(Ac)=Molecular weight of the acetyl ester, (C₂H₃O=43.045)

MW_(Bu)=Molecular weight of the butyryl ester, (C₄H₇O=71.095)

MW_(OH)=Molecular weight of the hydroxyl group, (OH=17.007)

MW_(AcKet)=Molecular weight of the acetyl ester minus one hydrogen,(C₂H₂O=42.037)

MW_(BuKet)=Molecular weight of the acetyl ester minus one hydrogen,(C₄H₆O=70.091)

MW_(anhydroglu)=Molecular weight of the anhydroglucose unit,(C₆H₁₀O₅=162.141)

DS_(Max)=Maximum degree of substitution (DS_(Max) is assumed to be 3.22for all calculations, to be more accurate, the degree of polymerizationshould be determined and the DS_(Max) used in the calculations should beappropriately adjusted. To simplify the calculations, a DS_(Max) of 3.22is assumed. As is evidenced by the negative values of Wt % Hydroxyl forseveral of the HS-CAB samples that were isolated in the fully esterifiedstate, 3.22 is not completely accurate.

Wt. % Propionyl cannot be determined from DS data obtained by ¹H-NMRsince the peaks generated by the propionyl protons overlap with thosegenerated by the butyryl protons. As a result, it is always assumed thatthe peaks are generated by the ester of interest (i.e. a butyryl esterin the case of a CAB or a propionyl ester in the case of a CAP).

We use one of two methods to determine the degree of substitution (DS)of the inventive cellulose mixed esters and conventional celluloseesters.

Method 1 determines the degree of substitution of acetyl and of butyrylby analyzing the NMR spectrum and comparing the peak area of theintegrated alkyl ester protons with the peak area of the cellulosebackbone protons. According to this method, acetyl can be distinguishedfrom the higher esters such as butyryl or propionyl, but butyryl cannotbe distinguished from propionyl. As a result, one must assume that allthe higher esters peaks come from either butyryl or propionyl, dependingupon the anhydride used. This is a reasonable assumption for celluloseacetate butyrates since the level of propionyl in CAB's is near zerowhen butyric anhydride is a reactant. Another issue is that with thismethod, ¹H-NMR does not indicate the degree of substitution of hydroxylgroups. The accepted method for determining the degree of substitutionof hydroxyl groups is by difference, that is, one assumes a maximumdegree of substitution and from that number subtracts the degree ofsubstitution of acetyl and butyryl. The result is the degree ofsubstitution of hydroxyl groups, seen in the following equation 1.DS_(Max)−DS_(Bu)−DS_(Ac)=DS_(OH)  Equation 1

Ester substitutions for conventional molecular weight cellulose estersare easily calculated. Since they have a higher degree of substitution,it is accepted that the DS_(Max) is 3.0. For the inventive mixed estersaccording to the invention, the maximum degree of substitution isgreater than 3.0 and is on a steeper part of the curve, that is smallchanges in DP have a greater impact on DS_(Max) than is seen withconventional esters. As a result, in order to obtain an accurate measureof the DS_(Max) and ultimately the DS_(OH), one should first determinethe degree of polymerization (based on molecular weight), and use thatinformation to determine the DS_(Max). Throughout this application, theDS_(Max) is assumed to be equal to 3.22 for this purpose. This is areasonable number that would be obtained with a degree of polymerizationof anhydroglucose units equal to 9. Unfortunately, DS_(Max)=3.22 is notan accurate assumption for all HS-CAB samples, and in some cases (seeExamples 9-27) the calculated DS_(OH) would be less than zero. Wetherefore sometimes describe an upper hydroxyl content of the cellulosemixed esters according to the invention, while omitting the lower value.

Method 2 utilizes the weight percent data determined by GC (acetyl,propionyl, and butyryl) and by titration (hydroxyl), and DS values arecalculated from these data. The uncertainty with the use of this methodis that the DS calculations are dependent on the accuracy and precisionof the GC and titration test methods. As a result, in some cases whenthis method is used to determine degree of substitution, the calculatedDS_(Max) is less than 3.0.

We are presenting both wt % and degree of substitution in theapplication, in certain instances, in an effort to describe theinventive esters as completely as possible. Unless stated otherwise, DSresults are from NMR data, wt % acetyl, propionyl and butyryl are fromgas chromatography analysis, and wt % hydroxyl values are from titrationdata.

The acid number of any carboxy(C₁-C₃)alkylcellulose esters aredetermined by titration as follows. An accurately weighed aliquot(0.5-1.0 g) of the carboxy (C₁-C₃) alkylcellulose ester is mixed with 50mL of pyridine and stirred. To this mixture is added 40 mL of acetonefollowed by stirring. Finally, 20 mL of water is added and the mixturestirred again. This mixture is titrated with 0.1 N sodium hydroxide inwater using a glass/combination electrode. A blank consisting of 50 mLof pyridine, 40 mL of acetone, and 20 mL of water is also titrated. Theacid number is calculated as follows where:

-   -   Ep=mL NaOH solution to reach end point of sample    -   B=mL NaOH solution to reach end point of blank    -   N=normality of sodium hydroxide solution    -   Wt.=weight of carboxy (C₁-C₃) alkylcellulose ester titrated.        Acid Number (mg KOH/g sample)=((Ep−B)*N*56.1)/Wt.

IV Test Method

The inherent viscosity (IV) of the cellulose esters described in thisapplication, except where indicated otherwise, are determined bymeasuring the flow time of a solution of known polymer concentration andthe flow time of a solvent-blank in a capillary viscometer, and thencalculating the IV.

IV is defined by the following equation:

${(n)\;\begin{matrix}{25{^\circ}\mspace{14mu}{C.}} \\{0.50\%}\end{matrix}} = \frac{\ln\frac{ts}{to}}{C}$

-   -   where:    -   (n)=Inherent Viscosity at 25° C. at a polymer concentration of        0.50 g/100 mL of solvent.    -   ln=Natural logarithm    -   t_(s)=Sample flow time    -   t_(o)=Solvent−blank flow time    -   C=Concentration of polymer in grams per 100 mL of solvent=0.50

Samples are prepared to a concentration of 0.50 g per 100 mL of solvent(60% phenol and 40% 1,1,2,2-tetrachloroethane by weight, also describedherein as “PM95”). The sample (0.25 g) is weighed into a culture tubecontaining a stir bar. 50.0 mL of 60% phenol and 40%1,1,2,2-tetrachloroethane by weight (also described in the applicationas “PM95”) is added. The mixture is placed in a heater and heated withstirring (300 rpm) to 125° C. (7 minutes to reach the target temperatureand 15 minute hold at 125° C.). The sample is allowed to cool to roomtemperature (25° C.) and is then filtered and placed in the viscometer(Model AVS 500-Schott America, Glass & Scientific Products, Inc.,Yonkers, N.Y.). IV is calculated according to the equation above.

Solution Viscosity Determination

A few solution viscosity values are provided in the present application,because the method has been used in the literature to measure viscosity,and inferentially, molecular weight. We note, however, that solutionviscosity measurements of the low molecular weight esters of theinvention are less meaningful than are the inherent viscositymeasurements as set forth above. We therefore provide solution viscositymeasurements for comparison purposes only, and not as a preferred methodof inferring molecular weight. Unless otherwise indicated, solutionviscosity values are measured according to ASTM-D 817.

GPC Method for Molecular Weight Determination

The molecular weight distributions of cellulose ester andcarboxy(C₁-C₃)alkylcellulose ester samples are determined by gelpermeation chromatography (GPC) using one of two methods listed below.

Method 1, THF: The molecular weight distributions of cellulose estersamples indicated as being tested by GPC with THF as a solvent aredetermined at ambient temperature in Burdick and Jackson GPC-grade THFstabilized with BHT, at a flow rate of 1 ml/min. All other samples aredetermined using GPC with NMP as a solvent, as set forth in Method 2below. Sample solutions are prepared by dissolution of about 50 mg ofpolymer in 10 ml of THF, to which 10 μl of toluene is added as aflow-rate marker. An autosampler is used to inject 50 μl of eachsolution onto a Polymer Laboratories PLgel® column set consisting of a 5μm Guard, a Mixed-C® and an Oligopore® column in series. The elutingpolymer is detected by differential refractometry, with the detectorcell held at 30° C. The detector signal is recorded by a PolymerLaboratories Caliber® data acquisition system, and the chromatograms areintegrated with software developed at Eastman Chemical Company. Acalibration curve is determined with a set of eighteen nearlymonodisperse polystyrene standards with molecular weight from 266 to3,200,000 g/mole and 1-phenylhexane at 162 g/mole. The molecular weightdistributions and averages are reported either as equivalent polystyrenevalues or as true molecular weights calculated by means of a universalcalibration procedure with the following parameters:

-   -   K_(PS)=0.0128 a_(PS)=0.712    -   K_(CE)=0.00757 a_(CE)=0.842

Method 2, NMP: The molecular weight distributions of all samples nototherwise indicated are determined by GPC with NMP as a solvent, asfollows. The molecular weight distributions of cellulose ester samplesare determined by gel permeation chromatography at 40° C. in Burdick andJackson N-Methylpyrrolidone with 1% Baker glacial acetic acid by weight,at a flow rate of 0.8 ml/min. Sample solutions are prepared bydissolution of about 25 mg of polymer in 10 ml of NMP, to which 10 μl oftoluene is added as a flow-rate marker. An autosampler is used to inject20 μl of each solution onto a Polymer Laboratories PLgel® column setconsisting of a 10 μm Guard, a Mixed-B® column. The eluting polymer isdetected by differential refractometry, with the detector cell held at40° C. The detector signal is recorded by a Polymer LaboratoriesCaliber® data acquisition system, and the chromatograms are integratedwith software developed at Eastman Chemical Company. A calibration curveis determined with a set of eighteen nearly monodisperse polystyrenestandards with molecular weight from 580 to 3,200,000 g/mole. Themolecular weight distributions and averages are reported as equivalentpolystyrene values.

The invention can be further illustrated by the following examples ofpreferred embodiments, although it will be understood that theseexamples are included merely for purposes of illustration and are notintended to limit the scope of the invention unless otherwisespecifically indicated.

EXAMPLES Example 1 Preparation of a Mid-Butyryl Cellulose Ester(HS-CAB-38) According to the Invention

Cellulose (80 g), provided as a dissolving grade of softwood pulp withan α-cellulose content of at least 94%, was activated by soaking inwater (˜1000 mL) in excess of 20 minutes, and then filtering through afritted funnel to remove the water. Residual water was removed bywashing the water-wet cellulose with acetic acid (˜2000 mL). The aceticacid-wet cellulose was then washed with butyric acid (˜2000 mL). A 2L-reaction kettle was charged with the butyric acid-wet activatedcellulose (311.67 g). Butyric acid (145.8 g) was added to the kettle.The mixture was cooled to 15° C. A mixture of butyric anhydride (225.9g), acetic anhydride (96.8 g), and sulfuric acid (3.42 g) were cooled to15° C. and then added to the reaction kettle. The mixture was stirredfor 1 hour at room temperature. The mixture was then heated to 84.2° C.and stirred for 11.5 hours. A mixture of water (150 g) and acetic acid(105 g) was slowly added to the clear “dope.” The mixture was stirredfor 7.5 hours at 65° C. The catalyst was neutralized by the addition ofMg(OAc)₄ (4.5 g) and NaOAc (1.7 g) dissolved in acetic acid (HOAc) (5.25g) and water (19 g). The neutralized dope was filtered at approximately50° C. through a glass wool-covered coarse fritted funnel. The productwas precipitated by pouring, with rapid mixing, the clear, neutralizeddope into 20-30 volumes of water. Decanting away the filtration liquidand adding fresh deionized water and then allowing the precipitate tostand in the fresh water for several hours hardened the precipitate. Theprecipitate was washed extensively with deionized water for at least 4hours. The product was dried in a vacuum oven at approximately 50° C.overnight to yield 95 g of the final product. The product had thefollowing composition: DS_(Bu)=1.92; DS_(Ac)=0.98; M_(n)=3012;M_(w)=5296; Polydispersity=1.758; IV (PM95)=0.077; S=38.2 ppm; Mg=12.9ppm; Na=9.7 ppm [Calculated results: wt. % Bu=40.40%, wt. % Ac=12.48%,wt. % OH=1.61%].

Example 2 Preparation of a Mid-Butyryl Cellulose Ester (HS-CAB-38)According to the Invention

Cellulose (80 g), provided as a dissolving grade of softwood pulp withan α-cellulose content of at least 94%, was activated by soaking inwater (˜1000 mL) for at least 20 minutes and then filtering through afritted funnel to remove the water. Residual water was removed bywashing the water-wet cellulose with acetic acid (˜2000 mL). The aceticacid-wet cellulose was then washed with butyric acid (˜2000 mL). A 2L-reaction kettle was charged with the butyric acid-wet activatedcellulose (415 g). Butyric acid (46.6 g) was added to the kettle. Themixture was cooled to 15° C. A mixture of butyric anhydride (246.4 g),acetic anhydride (98.8 g), and sulfuric acid (3.42 g) were cooled to 15°C. and then added to the reaction kettle. The mixture was stirred for 1hour at room temperature. The mixture was then heated to 78.3° C. andstirred for 11.2 hours. A mixture of water (156 g) and acetic acid (109g) was slowly added to the clear “dope.” The mixture was stirred for 7.5hours at 65° C. The catalyst was neutralized by the addition of Mg(OAc)₄(4.5 g) and NaOAc (1.7 g) dissolved in HOAc (5.25 g) and water (19 g).The neutralized dope was filtered at approximately 50° C. through aglass wool-covered coarse fritted funnel. The product was precipitatedby pouring, with rapid mixing, the clear, neutralized dope into 20-30volumes of water. Decanting away the filtration liquid and adding freshdeionized water and then allowing the precipitate to stand in the freshwater for several hours hardened the precipitate. The precipitate waswashed extensively with deionized water for at least 4 hours. Theproduct was dried in a vacuum oven at approximately 50° C. overnight toyield 132 g of the final product. The product had the followingcomposition: DS_(Bu)=1.78; DS_(Ac)=1.04; M_(n)=4448; M_(w)=9691;Polydispersity=2.179; IV (PM 95)=0.121; S=81.2 ppm; Mg=37.1 ppm; Na=23.3ppm. [Calculated results: wt. % Bu=38.28%, wt. % Ac=13.54%, wt. %OH=2.06%].

Example 3 Preparation of a High-Butyryl Cellulose Ester (HS-CAB-55)According to the Invention

Cellulose (80 g), provided as a dissolving grade of softwood pulp withan α-cellulose content of at least 94%, was activated by soaking inwater (˜1000 mL) for at least 20 minutes and then filtering through afritted funnel to remove the water. Residual water was removed bywashing the water-wet cellulose with acetic acid (˜2000 mL). The aceticacid-wet cellulose was then washed with butyric acid (˜2000 mL). A 2L-reaction kettle was charged with the butyric acid-wet activatedcellulose (390.33 g). Butyric acid (70.3 g) was added to the kettle. Themixture was cooled to 15° C. A mixture of butyric anhydride (396.1 g),acetic anhydride (0 g), and sulfuric acid (3.24 g) were cooled to 15° C.and then added to the reaction kettle. The mixture was stirred for 1hour at room temperature. The mixture was then heated to 87.4° C. andstirred for 11.0 hours. A mixture of water (164 g) and acetic acid (115g) was slowly added to the clear “dope.” The mixture was stirred for 23hours at 65° C. The catalyst was neutralized by the addition of Mg(OAc)₄(4.3 g) and NaOAc (1.6 g) dissolved in HOAc (5.25 g) and water (19 g).The neutralized dope was filtered at approximately 50° C. through aglass wool-covered coarse fritted funnel. The product was precipitatedby pouring, with rapid mixing, the clear, neutralized dope into 20-30volumes of water. Decanting away the filtration liquid and adding freshdeionized water and then allowing the precipitate to stand in the freshwater for several hours hardened the precipitate. The precipitate waswashed extensively with deionized water for at least 4 hours. Theproduct was dried in a vacuum oven at approximately 50° C. overnight toyield 110 g of the final product. The product had the followingcomposition: DS_(Bu)=2.66; DS_(Ac)=0.09; M_(n)=3492; M_(w)=6170;Polydispersity=1.767; IV (PM 95)=0.086; S=44 ppm; Mg=7.7 ppm; Na=6.9ppm. [Calculated results: wt. % Bu=53.67%, wt. % Ac=1.10%, wt. %OH=2.27%].

Example 4 Preparation of a High-Butyryl Cellulose Ester (HS-CAB-55)According to the Invention

Cellulose (80 g), provided as a dissolving grade of softwood pulp withan α-cellulose content of at least 94%, was activated by soaking inwater (˜1000 mL) for at least 20 minutes and then filtering through afritted funnel to remove the water. Residual water was removed bywashing the water-wet cellulose with acetic acid (˜2000 mL). The aceticacid-wet cellulose was then washed with butyric acid (˜2000 mL). A 2L-reaction kettle was charged with the butyric acid-wet activatedcellulose (346.0 g). Butyric acid (112.8 g) was added to the kettle. Themixture was cooled to 15° C. A mixture of butyric anhydride (399.0 g),acetic anhydride (0 g), and sulfuric acid (3.24 g) were cooled to 15° C.and then added to the reaction kettle. The mixture was stirred for 1hour at room temperature. The mixture was then heated to 82.6° C. andstirred for 11.0 hours. A mixture of water (164 g) and acetic acid (115g) was slowly added to the clear “dope.” The mixture was stirred for 23hours at 65° C. The catalyst was neutralized by the addition of Mg(OAc)₄(4.3 g) and NaOAc (1.6 g) dissolved in HOAc (5.25 g) and water (19 g).The neutralized dope was filtered at approximately 50° C. through aglass wool-covered coarse fritted funnel. The product was precipitatedby pouring, with rapid mixing, the clear, neutralized dope into 20-30volumes of water. Decanting away the filtration liquid and adding freshdeionized water and then allowing the precipitate to stand in the freshwater for several hours hardened the precipitate. The precipitate waswashed extensively with deionized water for at least 4 hours. Theproduct was dried in a vacuum oven at approximately 50° C. overnight toyield 136 g of the final product. The product had the followingcomposition: DS_(Bu)=2.62; DS_(Ac)=0.05; M_(n)=4137; M_(w)=8715;Polydispersity=2.106; IV (PM 95)=0.111; S=174.1; Mg=79.5; Na=65.1[Calculated results: wt. % Bu=53.55%, wt. % Ac=0.62%, wt. % OH=2.69%].

Example 5 Preparation of a Fully-Esterified, Low-Butyryl Cellulose Ester(HS-CAB-17) According to the Invention

A 2 L-reaction kettle was charged with a butyric acid-wet,water-activated cellulose (457.14 g), prepared according to Example 1.Butyric acid (18.10 g) and acetic acid (55.58 g) were added to thekettle. The mixture was cooled to 0° C. A mixture of butyric anhydride(572.00 g), acetic anhydride (145.60 g), and sulfuric acid (5.28 g) werecooled to −15° C. and then added to the reaction kettle. The mixture wasstirred for 1 hour at room temperature. The mixture was then heated to62.8° C. and stirred for 24 hours. The catalyst was neutralized by theaddition of Mg(OAc)₄ (42.29 g) dissolved in HOAc (500 g) and water (500g). The product was precipitated by pouring the clear, neutralized dopewith rapid mixing, into 20-30 volumes of water. The precipitate waswashed extensively with deionized water for at least 4 hours. Theproduct was dried in a vacuum oven at approximately 50° C. overnight.The product had the following composition: DS_(Bu)=1.07; DS_(Ac)=2.22;DS_(Max)=3.29; M_(n)=5575; M_(w)=10969; Polydispersity=1.97; IV (PM95)=0.122 [Calculated results: wt. % Bu=23.02%, wt. % Ac=28.92%, wt. %OH=−0.36%].

Example 6 Preparation of a Fully-Esterified Low-Butyryl Cellulose Ester(HS-CAB-17) According to the Invention

A 2 L-reaction kettle was charged with a butyric acid-wet,water-activated cellulose (457.14 g) (prepared according to Example 1).Butyric acid (18.10 g) and acetic acid (55.58 g) were added to thekettle. The mixture was cooled to 0° C. A mixture of butyric anhydride(572.00 g), acetic anhydride (145.60 g), and sulfuric acid (5.28 g) werecooled to −15° C. and then added to the reaction kettle. The mixture wasstirred for 1 hour at room temperature. The mixture was then heated to79.4° C. and stirred for 21.2 hours. The catalyst was neutralized by theaddition of Mg(OAc)₄ (42.29 g) dissolved in HOAc (500 g) and water (500g). The product was precipitated by pouring the clear, neutralized dopewith rapid mixing, into 20-30 volumes of water. The precipitate waswashed extensively with deionized water for approximately 15 hours. Theproduct was dried in a vacuum oven at approximately 50° C. overnight.The product had the following composition: DS_(Bu)=1.13; DS_(Ac)=2.34;DS_(Max)=3.47; M_(n)=2837; M_(w)=4401; Polydispersity=1.55; IV (PM95)=0.062. [Calculated results: wt. % Bu=23.65%, wt. % Ac=29.65%, wt. %OH=−1.25%].

Example 7 Preparation of a Fully-Esterified Mid-Butyryl Cellulose Ester(HS-CAB-38) According to the Invention

A 2 L-reaction kettle was charged with a butyric acid-wet,water-activated cellulose (163.00 g), prepared according to Example 1.Butyric acid (13.70 g) was added to the kettle. The mixture was cooledto 0° C. A mixture of butyric anhydride (196.90 g), acetic anhydride(71.69 g), and sulfuric acid (2.64 g) were cooled to −15° C. and thenadded to the reaction kettle. The mixture was stirred for 1 hour at roomtemperature. The mixture was then heated to 71.1° C. and stirred for 2hours. The catalyst was neutralized by the addition of Mg(OAc)₄ (42.29g) dissolved in HOAc (500 g) and water (500 g). The product wasprecipitated by pouring the clear, neutralized dope with rapid mixing,into 20-30 volumes of water. The precipitate was washed extensively withdeionized water for at least 4 hours. The product was dried in a vacuumoven at approximately 50° C. overnight. The product had the followingcomposition: DS_(Bu)=1.91; DS_(Ac)=1.43; DS_(Max)=3.34; M_(n)=4031;M_(w)=10343; Polydispersity=2.57; IV (PM 95)=0.089. [Calculated results:wt. % Bu=38.13%, wt. % Ac=17.28%, wt. % OH=−0.57%].

Example 8 Preparation of a Fully-Esterified, High-Butyryl CelluloseEster (HS-CAB-55) According to the Invention

A 2 L-reaction kettle was charged with a butyric acid-wet,water-activated cellulose (338.70 g), prepared according to Example 1.Butyric acid (22.78 g) was added to the kettle. The mixture was cooledto 0° C. A mixture of butyric anhydride (614.41 g), acetic anhydride(0.61 g), and sulfuric acid (5.28 g) were cooled to −15° C. and thenadded to the reaction kettle. The mixture was stirred for 1 hour at roomtemperature. The mixture was then heated to 79.4° C. and stirred for 5hours. The catalyst was neutralized by the addition of Mg(OAc)₄ (42.29g) dissolved in HOAc (500 g) and water (500 g). The product wasprecipitated by pouring the clear, neutralized dope with rapid mixing,into 20-30 volumes of water. The precipitate was washed extensively withdeionized water for at least 4 hours. The product was dried in a vacuumoven at approximately 50° C. overnight. The product had the followingcomposition: DS_(Bu)=3.18; DS_(Ac)=0.04; DS_(Max)=3.22; M_(n)=5113;M_(w)=11977; Polydispersity=2.34; IV (PM 95)=0.111. [Calculated results:wt. % Bu=58.47%, wt. % Ac=0.45%, wt. % OH=0.00%].

Examples 9-27 HS-CAB Samples

According to Examples 9-27, additional HS-CAB's of a range ofcompositions are prepared and evaluated. The samples evaluated aredescribed in Tables 2-3, along with data from Examples 1-8 set forthabove, and are prepared as described generally elsewhere in thespecification and in Examples 1-8.

TABLE 2 HS-CAB Samples CAB Wt % Wt % Wt % Wt % IV Example # Type Bu DSBu Ac DS Ac Pr DS Pr OH DS OH (PM95) Mn Tg 1 HS-CAB- 40.40¹ 1.92 12.48²0.98 NA³ NA 1.61⁴  0.32⁵ 0.077 3012⁶ NM 38 2 HS-CAB- 38.28¹ 1.78 13.54²1.04 NA³ NA 2.06⁴  0.4⁵ 0.121 4448⁶ NM 38 3 HS-CAB- 53.67¹ 2.66 1.10²0.09 NA³ NA 2.27⁴  0.47⁵ 0.086 3492⁶ NM 55 4 HS-CAB- 53.55¹ 2.62 0.62²0.05 NA³ NA 2.69⁴  0.55⁵ 0.111 4137⁶ NM 55 5 HS-CAB- 23.02¹ 1.07 28.92²2.22 NA³ NA −0.36⁴ −0.07⁵ 0.122 5575⁶ NM 20 6 HS-CAB- 23.65¹ 1.13 29.65²2.34 NA³ NA −1.25⁴ −0.25⁵ 0.062 2837⁶ NM 20 7 HS-CAB- 38.13¹ 1.91 17.28²1.43 NA³ NA −0.57⁴ −0.12⁵ 0.089 4031⁶ NM 38 8 HS-CAB- 58.47¹ 3.18 0.45²0.04 NA³ NA 0.00⁴  0⁵ 0.111 5113⁶ NM 55 9 HS-CAB- 22.87 1.01 27.45 2.210.71 NA 0.81  0⁵ 0.071 1556  83.38 20 10 HS-CAB- 21.71 1.04 23.93 2.080.00 NA 1.32  0.1⁵ 0.074 1812  90.98 20 11 HS-CAB- 24.25 1.12 21.12 1.780 NA 2.31  0.32⁵ 0.091 1838  101.71 20 12 HS-CAB- 23.99 1.08 21.43 1.720 NA 3.23  0.42⁵ 0.091 2152  107.55 20 13 HS-CAB- 24.31 NM 20.79 NM 0.55NA 3.58 NM 0.093 1823  112.41 20 14 HS-CAB- 29.38 1.40 18.37 1.55 0.38NA 1.81  0.27⁵ 0.085 NM 100.80 29

TABLE 3 HS-CAB Samples CAB Wt % Wt % Wt % Wt % IV Example # Type Bu DSBu Ac DS Ac Pr DS Pr OH DS OH (PM95) Mn Tg 15 HS-CAB- 28.72 1.18 17.171.27 0.56 NA 3.83 0.77⁵ 0.111 NM 120.37 29 16 HS-CAB- 41.52 NM 12.52 NM0.33 NA 0.79 NM 0.079 2040 85.03 38 17 HS-CAB- 39.73 1.99 11.50 1.060.37 NA 1.13 0.17⁵ 0.086 2340 95.06 38 18 HS-CAB- 38.16 NM 13.06 NM 0.41NA 1.4 NM 0.102 2734 102.72 38 19 HS-CAB- 39.51 1.51 11.21 0.95 0.28 NA2.16 0.76⁵ 0.095 2465 NM 38 20 HS-CAB- 35.01 1.63 13.42 0.94 0.77 NA3.51 0.65⁵ 0.103 NM 115.92 38 21 HS-CAB- 47.36 2.40 6.44 0.46 0.42 NA2.23 0.36⁵ NM 2499 80.72 46 22 HS-CAB- 44.18 2.13 7.24 0.49 0.5 NA 3.10.60⁵ 0.112 3182 99.17 46 23 HS-CAB- 53.88 2.91 2.52 0.13 0.33 NA 1.090.18⁵ 0.076 NM 75.27 55 24 HS-CAB- 54.10 2.91 2.21 0.19 0.33 NA 1.190.12⁵ 0.077 2265 76.07 55 25 HS-CAB- 51.82 NM 2.85 NM 0.44 NA 2.49 NM0.107 3222 92.25 55 26 HS-CAB- 54.59 2.38 2.36 0.13 0.36 NA 3.10 0.71⁵0.101 2783 99.17 55 27 HS-CAB- 45.39 2.11 3.56 0.18 0.41 NA 4.61 0.93⁵NM NM 114.43 55 ¹Wt. % Butyryl is calculated using the followingequation: Wt. % Bu = (DS_(Bu) * MW_(Bu))/((DS_(Ac) * MW_(AcKet)) +(DS_(Bu) * MW_(BuKet)) + MW_(anhydroglu)) ²Wt. % Acetyl is calculatedusing the following equation: Wt. % Ac = (DS_(Ac) * MW_(Ac))/((DS_(Ac) *MW_(AcKet)) + (DS_(Bu) * MW_(BuKet)) + MW_(anhydroglu)) ³DS_(Pr) cannotbe distinguished from butyryl from DS data obtained by ¹H-NMR, since thepeaks generated by the propionyl protons overlap with those generated bythe butyryl protons. As a result, it is assumed that the peaks aregenerated by the ester of interest (i.e. a butyryl ester in the case ofa CAB or a propionyl ester in the case of a CAB. ⁴Wt. % Hydroxyl iscalculated using the following equation: Wt. % OH = (DS_(Max) − DS_(Ac)− DS_(Bu)) * MW_(OH)/((DS_(Ac) * MW_(AcKet)) + (DS_(Bu) * MW_(BuKet)) +MW_(anhydroglu)) ⁵DS_(OH) is calculated using the following equation:DS_(OH) = DS_(Max) − DS_(Ac) − DS_(Bu) ⁶These GPC results are obtainedusing NMP as the solvent as opposed to THF. There is a bias betweenthese two methods and NMP results tend to be higher than those in THF.DS_(Ac) = Degree of substitution of butyryl as determined by ¹H-NMRDS_(Bu) = Degree of substitution of butyryl as determined by ¹H-NMRMW_(Ac) = Molecular weight of the acetyl ester, (C₂H₃O = 43.045) MW_(Bu)= Molecular weight of the butyryl ester, (C₄H₇O = 71.095) MW_(OH) =Molecular weight of the hydroxyl group, (OH = 17.007) MW_(AcKet) =Molecular weight of the acetyl ester minus one hydrogen, (C₂H₂O =42.037) MW_(BuKet) = Molecular weight of the acetyl ester minus onehydrogen, (C₄H₆O = 70.091) MW_(anhydroglu) = Molecular weight of theanhydroglucose unit, (C₆H₁₀O₅ = 162.141) DS_(Max) = Maximum degree ofsubstitution (DS_(Max) is assumed to be 3.22 for all calculations, to bemore accurate, the degree of polymerization could be determined and theDS_(Max) used in the calculations appropriately adjusted. To simplifythe calculations, a DS_(Max) of 3.22 is assumed. As is evidenced by thenegative values of Wt % Hydroxyl for several of the HS-CAB samplesisolated in the fully esterified state, 3.22 is not completely accurate.NA = Not available from data collected NM = Not measured

Examples 28-30 and Comparative Examples 31-33

The HS-CAB samples and commercial CAB samples (available from EastmanChemical Company), as set forth in Table 4, are dissolved in a varietyof solvents and solvent blends (see Table 5 and 6) at 10% by weight atapproximately 22° C. (72° F.) (room temperature). The samples arechecked visually for solubility and rated as soluble-clear (9),soluble-slight haze (7), gels (5), partially soluble (3), and insoluble(1). The inventive cellulose esters are considerably more soluble insome solvents than current commercial cellulose esters of similaracetyl/butyryl content (e.g. CAB-381-0.1, CAB-551-0.01, and CAB-171-15,all available from Eastman Chemical Company, Kingsport, Tenn.),particularly the HS CAB-38 and HS CAB-17 type ester for the followingsolvents: toluene, methanol, ethanol, isopropyl alcohol, Eastman EB,Eastman EP, PB, PP, DIBK, C-11 ketone, EB acetate, PM acetate, andn-butyl acetate.

TABLE 4 Properties of HS-CAB's evaluated Sample # 1 2 3 4 5 6 Ester TypeHS-CAB-38 HS-CAB-55 HS-CAB-17* HS-CAB-38 HS-CAB-55 HS-CAB-55 % Acetyl(GC)   9.99   2.93  24.85 NA NA NA % Butyryl (GC)  41.07  51.41  20.42NA NA NA % Propionyl   0.28   0.41   0.38 NA NA NA (GC) % Hydroxyl  1.40   2.2   3.83 NA NA NA (titration) DS Acetyl   1.00   0.07   1.70  1.00   0.07   0.05 (NMR) DS Butyryl   2.06   2.73   0.91   1.94   2.70  2.72 (NMR) DS CM   0   0   0   0   0   0 IV (PM 95)   0.096   0.088  0.091   0.096   0.088   0.119 M_(n) 1775^(†) 2274^(†) 2529^(†)3175^(††) 3349^(††) 4098^(††) M_(w) 3159^(†) 3636^(†) 3998^(†) 5551^(††)6066^(††) 8149^(††) ^(†)Calculated by GPC w/ THF as solvent.^(††)Calculated by GPC w/ NMP as solvent. ⁺⁺These three samples (Samples4-6) are blends of multiple runs, made according to Examples 1, 3, and4, respectively MEK = methyl ethyl ketone, MPK = methyl propyl ketone,MAK = methyl amyl ketone, PM acetate = propylene glycol methyl acetate,EB acetate = ethylene glycol butyl acetate, PM = propylene glycolmonomethyl ether, DM = diethylene glycol methyl ether, PB = propyleneglycol monobutyl ether, DE = diethylene glycol ethyl ether, PP =propylene glycol monopropyl ether, Eastman EP Solvent = ethylene glycolmonopropyl ether, Eastman EB Solvent = ethylene glycol monobutyl ether,95% Tecsol C = ethanol with methanol, MIBK and ethyl acetate asdenaturants with 5% water, NMP = n-methyl pyrrolidone, Eastman EEPSolvent = ethyl 3-ethoxypropionate

TABLE 5 Solubility of Cellulose Esters Solubility at 10 wt % solutions 1= insoluble, 3 = partially soluble, 5 = gels, Comparative ComparativeComparative 7 = soluble hazy, 9 = soluble Example 28 Example 31 Example29 Example 32 Example 30 Example 33 Esters--- HS-CAB-38 CAB 381-0.1HS-CAB-55 CAB 551-0.01 HS-CAB-17 CAB 171-15S Sample 1, Sample 2, Sample3, Table 4 Table 4 Table 4 Solvent: Blends: Toluene/Ethyl Acetate 70/309 9 9 9 5 1 Toluene/95% Tecsol C 80/20 9 9 9 9 5 1 Tecsol C(95)/EthylAcetate 70/30 9 9 9 9 7 1 Isopropyl Alcohol/Water 90/10 9 1 9 1 1 1MEK/MPK/MAK/EEP/n-Butyl Acetate 20/20/10/15/35 9 9 9 9 9 9 Ketones:Acetone 9 9 9 9 9 9 MEK 9 9 9 9 9 9 MPK 9 9 9 9 8 9 MAK 9 9 9 9 5 1 C-11ketone 9 1 9 9 3 1 DIBK 9 1 9 9 1 1 Esters: Ethyl Acetate 9 9 9 9 9 9n-Butyl Propionate 9 9 9 9 1 1 PM Acetate 9 9 9 9 9 3 EB Acetate 9 9 9 97 1 n-Butyl Acetate 9 9 9 9 7 1 t-Butyl Acetate (ester solvent) 9 9 9 93 1 n-Propyl Propionate 9 9 9 9 7 9

TABLE 6 Solubility of Cellulose Esters Solubility at 10 wt % solutions 1= insoluble, 3 = partially soluble, 5 = gels, Comparative ComparativeComparative 7 = soluble hazy, 9 = soluble Example 28 Example 31 Example29 Example 32 Example 30 Example 33 Esters--- HS-CAB-38 CAB 381-0.1HS-CAB-55 CAB 551-0.01 HS-CAB-17 CAB 171-15S Sample 1, Sample 2, Sample3, Table 4 Table 4 Table 4 Solvent: Glycol ethers: PM 9 9 9 9 9 1 DM 9 99 9 9 3 PB 7 1 7 9 3 1 DE 9 9 9 9 8 1 PP 9 1 9 9 5 1 EP 9 1 9 9 5 1 EB 91 9 9 3 1 Alcohols: Diacetone alcohol 9 9 9 9 9 9 Methanol 9 1 9 1 1 1Tecsol C (95) 9 1 9 1 3 1 Isopropyl alcohol 3 1 7 1 3 1 Other: EEP 9 9 99 7 1 Exxate 600 9 9 9 9 5 1 NMP 9 9 5 9 9 9 VM & P Naptha 3 1 3 1 3 1Toluene 9 1 9 5 3 1 Xylene 3 1 3 1 3 1 Dimethylaminoethanol 9 9 9 9 9 9Methylene chloride 9 9 9 9 9 9 Pyridine 9 9 9 9 9 9

Example 34 Viscosity Studies

The viscosities of an HS-CAB-38 (Sample 4, Table 4) and an HS-CAB-55(Sample 5, Table 4) are compared to the lowest viscosity commercialcellulose esters, CAB-381-0.1 and CAB-551-0.01, of comparable butyrylcontent, using as solvent an n-butyl acetate/xylene in a 90/10 by weightmixture, using Brookfield viscosity as a function of concentration. FIG.1 shows the relative viscosity at each measured concentration. Note howthe log viscosities vs. concentration plots are parallel for each of theesters. This indicates that each of the esters has a similar exponentialviscosity rise with concentration, except that the lower the molecularweight of the ester is, the higher the concentration becomes to displaythe same behavior. Because the inventive esters exhibit a lowerviscosity than conventional esters at the same concentration, they allowcoating formulations having a higher ester content at the targetviscosity.

Additional Brookfield viscosity data are presented in Table 6A. TheHS-CAB's evaluated are dissolved at various solids levels in n-butylacetate/xylene (9:1 by weight).

TABLE 6A Viscosity in a 90/10 by weight mixture of n-butylacetate/xylene IV % Material lot Wt % Bu Wt % OH (PM95) SolidsCentipoise HS-CAB-38 EMT02-121 39.77 1.61 0.09 30   12.2 HS-CAB-38EMT02-121 39.77 1.61 0.09 50  312 HS-CAB-38 EMT02-121 39.77 1.61 0.09 603430 HS-CAB-38 EMT02-121 39.77 1.61 0.09 70 70800  HS-CAB-38 EMT02-12238.48 1.66 0.08 30    12.6 HS-CAB-38 EMT02-122 38.48 1.66 0.08 50  332HS-CAB-38 EMT02-122 38.48 1.66 0.08 60 3655 HS-CAB-38 EMT02-122 38.481.66 0.08 70 88300  HS-CAB-55 EMT02-117 52.78 1.18 0.08 30    9.4HS-CAB-55 EMT02-117 52.78 1.18 0.08 50   139.4 HS-CAB-55 EMT02-117 52.781.18 0.08 60 200000*  HS-CAB-55 EMT02-117 52.78 1.18 0.08 70 200000* HS-CAB-55 EMT02-128 54.17 1.43 0.08 30    12.3 HS-CAB-55 EMT02-128 54.171.43 0.08 50   132.4 HS-CAB-55 EMT02-128 54.17 1.43 0.08 60  885HS-CAB-55 EMT02-128 54.17 1.43 0.08 70 200000*  HS-CAB-17 EMT02-084 20.12.18 0.08 30    37.6 HS-CAB-17 EMT02-084 20.1 2.18 0.08 50 2685HS-CAB-17 EMT02-084 20.1 2.18 0.08 60 65800  HS-CAB-17 EMT02-084 20.12.18 0.08 70 200000  HS-CAB-17 EMT02-085 20.1 2.18 0.08 30    45.5HS-CAB-17 EMT02-085 20.42 1.99 0.09 50 5660 HS-CAB-17 EMT02-085 20.421.99 0.09 60 124800  HS-CAB-17 EMT02-085 20.42 1.99 0.09 70 **CAB-551-0.01 NA 55.06 1.50 0.26 10    3.8 CAB-551-0.01 NA 55.06 1.500.26 30  160 CAB-551-0.01 NA 55.06 1.50 0.26 40  935 CAB-551-0.01 NA55.06 1.50 0.26 50 10300  CAB-381-0.1 NA 39.87 1.61 0.44 10  38CAB-381-0.1 NA 39.87 1.61 0.44 30 1600 CAB-381-0.1 NA 39.87 1.61 0.44 4015300  CAB-381-0.1 NA 39.87 1.61 0.44 50 508000  HS-CAB-55 (EMT02-117)gels at 65, 67, 69, and 70% HS-CAB-55 (EMT02-128) gels at 70% HS-CAB-17(EMT02-084) gels at 70% HS-CAB-17 (EMT02-085) gels at 60% and 70%HS-CAB-38 (EMT02-121) is very viscous at 70% HS-CAB-38 (EMT02-122) isvery viscous at 70% HS-CAB-17 (EMT02-084) is very viscous at 60%*Mixture gels **Not measured since material is partially insoluble

Examples 35-40 and Comparative Examples 41-46 Viscosity of HS CAB/ResinBlends and Comparison with Conventional CAB/Resin Blends

Blends of HS-CAB-38 (Sample 1, Table 4) and HS-CAB-55 (Sample 2, Table4) with commercial resins (Duramac HS 2706, Polymac HS 5776, andAcrylamac 232-1700) (1:1 CAB to resin, at 20% and 40% solids levels) areprepared and the viscosities of the solutions are determined using aBrookfield viscometer. Comparison blends of CAB-381-0.1 and CAB-551-0.01with commercial resins (Duramac HS 2706, Polymac HS 5776, and Acrylamac232-1700) (1:1 CAB to resin, at 20% solids levels) are prepared and theviscosities of the solutions are determined using a Brookfieldviscometer. The results are presented in Table 7. The HS-CABs have verylittle impact on solution or spray viscosity and can thus be added atmuch higher levels than conventional esters. This results in an increasein the % non-volatiles in the system.

TABLE 7 Viscosity of CABs for High DS_(Max), low DP and ConventionalCAB/Resin Blends Example # CAB Type Resin Type Ratio of CAB:Resin TotalSolids Spindle # RPM Viscosity (cP) 35 HS-CAB-38 Duramac HS 2706 1:1 40%18 30 13.3 41 CAB-381-0.1 Duramac HS 2706 1:1 20% 18 30 23.7 36HS-CAB-55 Duramac HS 2706 1:1 40% 18 30 12.8 42 CAB-551-0.01 Duramac HS2706 1:1 20% 18 60 6.0 37 HS-CAB-38 Polymac HS 5776 1:1 40% 18 30 15.443 CAB-381-0.1 Polymac HS 5776 1:1 20% 18 30 24.5 38 HS-CAB-55 PolymacHS 5776 1:1 40% 18 30 13.9 44 CAB-551-0.01 Polymac HS 5776 1:1 20% 18 605.9 39 HS-CAB-38 Acrylamac 232-1700 1:1 40% 18 30 37.4 45 CAB-381-0.1Acrylamac 232-1700 1:1 20% 18 30 31.9 40 HS-CAB-55 Acrylamac 232-17001:1 40% 18 30 32.9 46 CAB-551-0.01 Acrylamac 232-1700 1:1 20% 18 60 8.4

Example 47 Compatibility of HS-CAB's with Various Coatings Resins

Solutions are prepared using ratios of cellulosic to modifying resin of1/9, 1/3, 1/1, and 3/1 at 10% solids in a mixture of n-butylacetate/MEK/MPK/EEP/MAK (35/20/20/15/10). Films are cast on glass at 10mil thickness. The films are allowed to air dry for 24 hours. Theresulting films are evaluated visually under good room lights (Tables 8and 9) for film clarity. HS-CAB-55 (Sample 2, Table 4) and HS-CAB-38(Sample 1, Table 4) have good compatibility with most resins tested:acrylics, polyesters, melamine type resins, urea formaldehyde resins,alkyds, isocyanate resin, phenolics and epoxies, and limitedcompatibility in vinyls and polyamides. HS-CAB-17s (Sample 3, Table 4)are less compatible than HS-CAB-55 and HS-CAB-38, but still can be usedwith the resins tested in limited amounts.

This example shows the compatibility of the inventive cellulose mixedesters with a variety of coatings resins.

TABLE 8 Compatibility Studies Film Compatibility, 1 mil films cast from10 mil thickness from 10% solution from a solvent blend ofMEK/MPK/MAK/EEP/n-BuOAc (20/20/10/15/35) HS-CAB-55 HS-CAB-38 HS-CAB-20Sample: TYPE RESIN EMT02-82 EMT02-83 EMT02-85 R&H Acryloid AT954 1:4THERMOSET 0 0 1 ACRYLIC 1:1 0 0 9 4:1 0 0 7 R&H Acryloid B-44 1:4ACRYLIC 0 0 9 LACQUER 1:1 0 7 7 4:1 0 0 0 R&H Paraloid A-21 1:4 ACRYLIC0 0 0 LACQUER 1:1 0 0 9 4:1 0 0 7 Cytec CYMEL 303 1:4 HEXAMETHOXYMETHYL0 0 0 MELAMINE 1:1 0 0 7 4:1 0 0 7 ELVACITE 2008 1:4 DUPONT ACRYLIC 0 00 LACQUER 1:1 Methyl methacrylate 0 0 7 (lo MW) 4:1 0 0 7 PolymacHS220-2010 1:4 Polyester 0 0 0 1:1 0 0 0 4:1 0 0 0 BEETLE 65 1:4 CytecUrea 0 7 0 Formadehyde 1:1 0 0 0 4:1 7 7 0 UCAR VYHD 1:4 VINYL 3 9 9CHLORIDE/VINYL ACETATE 1:1 3 9 9 4:1 3 7 1 CK-2103 1:4 UC PHENOLIC 0 0 01:1 0 0 0 4:1 0 0 0 R&H Paraloid WR97 1:4 RH WATER 0 0 7 REDUCIBLE TSACRYLIC 1:1 0 0 9 4:1 0 0 7 0 = clear, no haze; 1 = very slight haze,only in bright light; 3 = slight haze in room; 5 = translucent; 7 =translucent and incompatible domains; 9 = hazy and incompatible; 10 =opaque

TABLE 9 Compatibility Studies HS-CAB-55 HS-CAB-38 HS-CAB-20 Sample: TYPERESIN EMT02-82 EMT02-83 EMT02-85 Neat esters 1:0 Cellulosic resinswithout 0 0 0 resins R&H Acryloid AU608X R&H Acrylic 0 0 0 1:4 1:1 0 0 14:1 0 0 7 EPON 1001F 1:4 DUPONT EPOXY 5 5 5 1:1 5 5 9 4:1 3 5 7 VERSAMID750 1:4 POLYAMIDE 9 9 9 1:1 9 9 9 4:1 9 9 9 Duramac 207-2706 1:4 EASTMANshort oil, 0 0 0 TOFA, 23% n-butac, corrosion resistant 1:1 0 0 0 4:1 00 0 Duramac 5205 1:4 Med. Coconut oil alkyd, 0 0 1 40% xylene.Plasticizer for NC 1:1 0 0 7 4:1 0 0 7 Duramac 51-5135 1:4 EASTMAN Medoil SOYA 0 5 7 alkyd gasoline resistant, 40% VMP 1:1 0 3 7 4:1 0 3 7Duramac 207-1405 1:4 EASTMAN SOYA chain 1 5 7 stopped alkyd, 50% NV 1:11 3 7 4:1 0 1 7 ELVACITE 2044 1:4 DuPont ethyl methacrylate 0 0 7 1:1 00 8 4:1 0 0 8 Des N 3300 1:4 Bayer Polymeric isocyanate 0 0 0 1:1 0 0 54:1 0 0 10

Example 48 HS-CAB Solubilities

Solutions are prepared using ratios of cellulosic to modifying resinratio of 1/1 at 10% solids in one of four solvent blends, Solvent 1(MEK/PMAc/EEP, 5/4/1), Solvent 2 (MEK/Xylene/EEP, 5/4/1), Solvent 3(MEK/PMAc/Toluene, 1/1/2), Solvent 4 (PMAc/EtOH/n-BuOH, 2/1/1). Filmsare cast on glass at 10 mil thickness. The films are allowed to air dryfor 24 hours. The resulting films are evaluated visually under good roomlights and the results are presented in Tables 10-16 for film clarity.

TABLE 10 Film Compatibility 1 mil films cast from 8 mil thickness from25% solution from 4 different solvent blends Resin R&H Eastman EastmanAcryloid Bayer R&H Acrylamac Acrylamac AT400 A670 AU608 2328 2350CAB:Resin 1:1 1:1 1:1 1:1 1:1 Solvent Solvent 1 Solvent 1 Solvent 1Solvent 1 Solvent 1 Type Resin OH OH Wt % Thermoset FunctionalFunctional Thermoset OH Functional Wt % Bu Wt % Ac OH Acrylic-1Acrylic-1 Acrylic-1 Acrylic-1 Acrylic-1 CAB 381- Commercial 39.87*12.90* 1.61* 0 0 0 1 0 0.1 CAB 551- Commercial 55.06* 1.07* 1.50* 0 0 00 0 0.01 HS-CAB-38 EMT02-158 39.51 11.21 2.16 0 0 0 0 3 HS-CAB-38EMT03-030 35.01 13.42 3.51 3 0 0 3 5 HS-CAB-38 EMT02-162 39.73 11.5 1.130 0 0 0 3 HS-CAB-55 EMT02-105 53.88 2.52 1.09 0 0 0 0 0 HS-CAB-55EMT02-117 54.1 2.21 1.19 0 0 0 0 0 HS-CAB-55 EMT02-131 54.59 2.36 3.1 00 0 1 0 HS-CAB-55 EMT02-133 51.82 2.85 2.49 0 0 0 0 0 HS-CAB-55EMT02-169 45.39 3.56 4.61 0 0 0 0 5 HS-CAB-46 EMT03-077 47.36 6.44 2.230 0 0 0 0 HS-CAB-46 EMT02-062 44.18 7.24 3.1 0 0 0 0 1 HS-CAB-29EMT03-059 28.72 17.17 3.83 5 3 0 9 9 HS-CAB-29 EMT03-051 29.38 18.371.81 1 1 0 9 9 HS-CAB-20 EMT03-042 21.71 23.93 1.32 9 9 5 9 9 HS-CAB-20EMT03-039 24.25 21.12 2.31 9 7 0 5 9 HS-CAB-20 EMT03-044 22.87 27.450.81 9 7 7 9 9 HS-CAB-20 EMT03-040 23.99 21.43 3.23 9 7 0 5 9 Solvent 1= MEK/PMAc/EEP 5/4/1 Solvent 2 = MEK/Xylene/EEP 5/4/1 Solvent 3 =MEK/PMAc/Toluene 1/1/2 Solvent 4 = PMAc/EtOH/n-BuOH 2/1/1 0 = clear nohaze; 1 = very slight have, only in bright light; 3 = slight haze inroom; 5 = translucent; 7 = translucent and incompatible domains; 9 =hazy and incompatible; 10 = opaque *Calculated using equationspreviously described in Examples 1-8.

TABLE 11 Film Compatibility 1 mil films cast from 8 mil thickness from25% solution from 4 different solvent blends Resin Eastman Akzo NobelEastman Eastman Eastman Reactol 175 Microgel Duramac 1205 Duramac 2706Duramac 2314 CAB:Resin 1:1 1:1 1:1 1:1 1:1 Solvent Solvent 1 Solvent 1Solvent 1 Solvent 1 Solvent 1 Type Resin Chain Stopped Hexamethoxy Wt %Wt % Thermoset Thermoset SOYA Oil methyl Styrenated Wt % Bu Ac OHAcrylic-1 Acrylic-1 alkyd-1 melamine-1 alkyd-1 CAB 381- Commercial39.87* 12.90* 1.61* 0 7 1 0 3 0.1 CAB 551- Commercial 55.06* 1.07* 1.50*0 5 3 0 0 0.01 HS-CAB-38 EMT02-158 39.51 11.21 2.16 0 0 1 0 0 HS-CAB-38EMT03-030 35.01 13.42 3.51 0 1 3 0 9 HS-CAB-38 EMT02-162 39.73 11.5 1.130 0 3 0 0 HS-CAB-55 EMT02-105 53.88 2.52 1.09 0 0 1 0 0 HS-CAB-55EMT02-117 54.1 2.21 1.19 0 0 3 0 0 HS-CAB-55 EMT02-131 54.59 2.36 3.1 00 0 0 0 HS-CAB-55 EMT02-133 51.82 2.85 2.49 0 0 0 0 0 HS-CAB-55EMT02-169 45.39 3.56 4.61 0 1 1 0 1 HS-CAB-46 EMT03-077 47.36 6.44 2.230 0 0 0 0 HS-CAB-46 EMT02-062 44.18 7.24 3.1 0 0 0 0 0 HS-CAB-29EMT03-059 28.72 17.17 3.83 0 3 3 0 9 HS-CAB-29 EMT03-051 29.38 18.371.81 0 1 5 0 9 HS-CAB-20 EMT03-042 21.71 23.93 1.32 0 3 9 9 9 HS-CAB-20EMT03-039 24.25 21.12 2.31 0 3 9 9 9 HS-CAB-20 EMT03-044 22.87 27.450.81 7 3 9 1 9 HS-CAB-20 EMT03-040 23.99 21.43 3.23 0 3 9 0 9 Solvent 1= MEK/PMAc/EEP 5/4/1 Solvent 2 = MEK/Xylene/EEP 5/4/1 Solvent 3 =MEK/PMAc/Toluene 1/1/2 Solvent 4 = PMAc/EtOH/n-BuOH 2/1/1 0 = clear nohaze; 1 = very slight have, only in bright light; 3 = slight haze inroom; 5 = translucent; 7 = translucent and incompatible domains; 9 =hazy and incompatible; 10 = opaque

TABLE 12 Film Compatibility 1 mil films cast from 8 mil thickness from25% solution from 4 different solvent blends Resin Resimene ResimeneDesmophen Bayer Desmodur Cytec CE-7103 755 1800 3300 Cymel 303 CAB:Resin1:1 1:1 1:1 1:1 1:1 Solvent Solvent 1 Solvent 1 Solvent 2 Solvent 2Solvent 2 Wt % Wt % Wt % Type Resin Bu Ac OH Melamine-1 Melamine-1Polyester-2 Isocyanate-2 Melamine-2 CAB 381- Commercial 39.87* 12.90*1.61* 0 0 0 5 0 0.1 CAB 551- Commercial 55.06* 1.07* 1.50* 0 0 0 0 00.01 HS-CAB-38 EMT02-158 39.51 11.21 2.16 0 0 0 0 0 HS-CAB-38 EMT03-03035.01 13.42 3.51 0 0 0 1 0 HS-CAB-38 EMT02-162 39.73 11.5 1.13 0 0 0 0 0HS-CAB-55 EMT02-105 53.88 2.52 1.09 0 0 0 0 0 HS-CAB-55 EMT02-117 54.12.21 1.19 0 0 0 0 0 HS-CAB-55 EMT02-131 54.59 2.36 3.1 0 0 0 0 0HS-CAB-55 EMT02-133 51.82 2.85 2.49 0 0 0 0 0 HS-CAB-55 EMT02-169 45.393.56 4.61 0 0 0 1 0 HS-CAB-46 EMT03-077 47.36 6.44 2.23 0 0 0 0 0HS-CAB-46 EMT02-062 44.18 7.24 3.1 0 0 0 0 0 HS-CAB-29 EMT03-059 28.7217.17 3.83 3 0 0 9 0 HS-CAB-29 EMT03-051 29.38 18.37 1.81 0 0 0 0 0HS-CAB-20 EMT03-042 21.71 23.93 1.32 9 9 7 7 0 HS-CAB-20 EMT03-039 24.2521.12 2.31 1 0 0 9 0 HS-CAB-20 EMT03-044 22.87 27.45 0.81 5 0 7 1 0HS-CAB-20 EMT03-040 23.99 21.43 3.23 5 0 7 9 0 Solvent 1 = MEK/PMAc/EEP5/4/1 Solvent 2 = MEK/Xylene/EEP 5/4/1 Solvent 3 = MEK/PMAc/Toluene1/1/2 Solvent 4 = PMAc/EtOH/n-BuOH 2/1/1 0 = clear no haze; 1 = veryslight have, only in bright light; 3 = slight haze in room; 5 =translucent; 7 = translucent and incompatible domains; 9 = hazy andincompatible; 10 = opaque

TABLE 13 Film Compatibility 1 mil films cast from 8 mil thickness from25% solution from 4 different solvent blends Resin Eastman EastmanPolymac HS Polymac HS Eastman Eastman 5789 5761 Duramac 5135 Duramac5731 CAB:Resin 1:1 1:1 1:1 1:1 Solvent Solvent 2 Solvent 2 Solvent 2Solvent 2 Type Resin Medium Medium Wt % SOYA oil SOYA oil Wt % Bu Wt %Ac OH Polyester-2 Polyester-2 alkyd-2 alkyd-2 CAB 381-0.1 Commercial39.87* 12.90* 1.61* 0 0 0 5 CAB 551- Commercial 55.06* 1.07* 1.50* 0 0 13 0.01 HS-CAB-38 EMT02-158 39.51 11.21 2.16 0 0 7 3 HS-CAB-38 EMT03-03035.01 13.42 3.51 0 0 9 7 HS-CAB-38 EMT02-162 39.73 11.5 1.13 0 0 7 3HS-CAB-55 EMT02-105 53.88 2.52 1.09 0 0 0 0 HS-CAB-55 EMT02-117 54.12.21 1.19 0 0 0 0 HS-CAB-55 EMT02-131 54.59 2.36 3.1 0 0 7 3 HS-CAB-55EMT02-133 51.82 2.85 2.49 0 0 0 3 HS-CAB-55 EMT02-169 45.39 3.56 4.61 00 9 9 HS-CAB-46 EMT03-077 47.36 6.44 2.23 0 0 1 3 HS-CAB-46 EMT02-06244.18 7.24 3.1 0 0 7 9 HS-CAB-29 EMT03-059 28.72 17.17 3.83 0 0 9 9HS-CAB-29 EMT03-051 29.38 18.37 1.81 0 0 7 7 HS-CAB-20 EMT03-042 21.7123.93 1.32 9 9 9 9 HS-CAB-20 EMT03-039 24.25 21.12 2.31 0 0 9 7HS-CAB-20 EMT03-044 22.87 27.45 0.81 9 9 7 7 HS-CAB-20 EMT03-040 23.9921.43 3.23 0 0 9 9 Solvent 1 = MEK/PMAc/EEP 5/4/1 Solvent 2 =MEK/Xylene/EEP 5/4/1 Solvent 3 = MEK/PMAc/Toluene 1/1/2 Solvent 4 =PMAc/EtOH/n-BuOH 2/1/1 0 = clear no haze; 1 = very slight have, only inbright light; 3 = slight haze in room; 5 = translucent; 7 = translucentand incompatible domains; 9 = hazy and incompatible; 10 = opaque

TABLE 14 Film Compatibility 1 mil films cast from 8 mil thickness from25% solution from 4 different solvent blends Resin Eastman Shell DowDuramac Epon DER Rhodia Bayer Desmodur 5359 1001F 542 XIDT IL CAB:Resin1:1 1:1 1:1 1:1 1:1 Solvent Solvent 2 Solvent 2 Solvent 2 Solvent 2Solvent 2 Type Resin Wt % Wt % Styrenated Bu Wt % Ac OH alkyd-2 Epoxy-2Epoxy-2 Isocyanate-2 Isocyanate-2 CAB 381-0.1 Commercial 39.87* 12.90*1.61* 9 5 0 3 9 CAB 551- Commercial 55.06* 1.07* 1.50* 0 0 0 0 10 0.01HS-CAB-38 EMT02-158 39.51 11.21 2.16 3 5 0 0 0 HS-CAB-38 EMT03-030 35.0113.42 3.51 9 5 0 5 0 HS-CAB-38 EMT02-162 39.73 11.5 1.13 3 5 0 0 0HS-CAB-55 EMT02-105 53.88 2.52 1.09 0 5 0 0 9 HS-CAB-55 EMT02-117 54.12.21 1.19 0 5 0 0 9 HS-CAB-55 EMT02-131 54.59 2.36 3.1 3 5 0 0 0HS-CAB-55 EMT02-133 51.82 2.85 2.49 0 3 0 0 3 HS-CAB-55 EMT02-169 45.393.56 4.61 9 3 0 3 0 HS-CAB-46 EMT03-077 47.36 6.44 2.23 0 3 0 0 0HS-CAB-46 EMT02-062 44.18 7.24 3.1 7 3 0 0 0 HS-CAB-29 EMT03-059 28.7217.17 3.83 9 9 3 9 0 HS-CAB-29 EMT03-051 29.38 18.37 1.81 7 5 0 3 0HS-CAB-20 EMT03-042 21.71 23.93 1.32 9 7 0 9 0 HS-CAB-20 EMT03-039 24.2521.12 2.31 9 3 0 9 0 HS-CAB-20 EMT03-044 22.87 27.45 0.81 9 7 0 9 0HS-CAB-20 EMT03-040 23.99 21.43 3.23 9 7 0 9 0 Solvent 1 = MEK/PMAc/EEP5/4/1 Solvent 2 = MEK/Xylene/EEP 5/4/1 Solvent 3 = MEK/PMAc/Toluene1/1/2 Solvent 4 = PMAc/EtOH/n-BuOH 2/1/1 0 = clear no haze; 1 = veryslight have, only in bright light; 3 = slight haze in room; 5 =translucent; 7 = translucent and incompatible domains; 9 = hazy andincompatible; 10 = opaque

TABLE 15 Film Compatibility 1 mil films cast from 8 mil thickness from25% solution from 4 different solvent blends Resin Eastman Carbamac UCCUCAR HS4372 VYHD UCAR VMCH CAB:Resin 1:1 1:1 1:1 Solvent Solvent 2Solvent 3 Solvent 3 Type Resin Vinyl Vinyl Wt % Wt % Wt % chloride/Vinylchloride/Vinyl Bu Ac OH Polyurethane-2 acetate-3 acetate-3 CAB 381-Commercial 39.87* 12.90* 1.61* 7 0.1 CAB 551- Commercial 55.06* 1.07*1.50* 9 0.01 HS-CAB-38 EMT02-158 39.51 11.21 2.16 1 7 7 HS-CAB-38EMT03-030 35.01 13.42 3.51 5 7 7 HS-CAB-38 EMT02-162 39.73 11.5 1.13 3 73 HS-CAB-55 EMT02-105 53.88 2.52 1.09 1 7 3 HS-CAB-55 EMT02-117 54.12.21 1.19 3 7 7 HS-CAB-55 EMT02-131 54.59 2.36 3.1 5 7 7 HS-CAB-55EMT02-133 51.82 2.85 2.49 3 7 3 HS-CAB-55 EMT02-169 45.39 3.56 4.61 7 77 HS-CAB-46 EMT03-077 47.36 6.44 2.23 3 7 3 HS-CAB-46 EMT02-062 44.187.24 3.1 7 7 7 HS-CAB-29 EMT03-059 28.72 17.17 3.83 5 7 3 HS-CAB-29EMT03-051 29.38 18.37 1.81 7 7 3 HS-CAB-20 EMT03-042 21.71 23.93 1.32 77 3 HS-CAB-20 EMT03-039 24.25 21.12 2.31 7 7 3 HS-CAB-20 EMT03-044 22.8727.45 0.81 7 3 3 HS-CAB-20 EMT03-040 23.99 21.43 3.23 7 7 3 Solvent 1 =MEK/PMAc/EEP 5/4/1 Solvent 2 = MEK/Xylene/EEP 5/4/1 Solvent 3 =MEK/PMAc/Toluene 1/1/2 Solvent 4 = PMAc/EtOH/n-BuOH 2/1/1 0 = clear nohaze; 1 = very slight have, only in bright light; 3 = slight haze inroom; 5 = translucent; 7 = translucent and incompatible domains; 9 =hazy and incompatible; 10 = opaque

TABLE 16 Film Compatibility 1 mil films cast from 8 mil thickness from25% solution from 4 different solvent blends Resin DuPont LVAX Henkle 40Verasmid 750 CAB:Resin 1:1 1:1 Solvent Solvent 3 Solvent 4 Type ResinVinyl Wt % chloride/Vinyl Wt % Bu Wt % Ac OH acetate-3 Polyamide-4 CAB381-0.1 Commercial 39.87* 12.90* 1.61* CAB 551- Commercial 55.06* 1.07*1.50* 0.01 HS-CAB-38 EMT02-158 39.51 11.21 2.16 3 5 HS-CAB-38 EMT03-03035.01 13.42 3.51 7 5 HS-CAB-38 EMT02-162 39.73 11.5 1.13 3 3 HS-CAB-55EMT02-105 53.88 2.52 1.09 5 3 HS-CAB-55 EMT02-117 54.1 2.21 1.19 5 5HS-CAB-55 EMT02-131 54.59 2.36 3.1 5 5 HS-CAB-55 EMT02-133 51.82 2.852.49 5 5 HS-CAB-55 EMT02-169 45.39 3.56 4.61 3 5 HS-CAB-46 EMT03-07747.36 6.44 2.23 5 5 HS-CAB-46 EMT02-062 44.18 7.24 3.1 5 3 HS-CAB-29EMT03-059 28.72 17.17 3.83 5 5 HS-CAB-29 EMT03-051 29.38 18.37 1.81 5 5HS-CAB-20 EMT03-042 21.71 23.93 1.32 5 5 HS-CAB-20 EMT03-039 24.25 21.122.31 5 5 HS-CAB-20 EMT03-044 22.87 27.45 0.81 5 7 HS-CAB-20 EMT03-04023.99 21.43 3.23 5 3 Solvent 1 = MEK/PMAc/EEP 5/4/1 Solvent 2 =MEK/Xylene/EEP 5/4/1 Solvent 3 = MEK/PMAc/Toluene 1/1/2 Solvent 4 =PMAc/EtOH/n-BuOH 2/1/1 0 = clear no haze; 1 = very slight have, only inbright light; 3 = slight haze in room; 5 = translucent; 7 = translucentand incompatible domains; 9 = hazy and incompatible; 10 = opaque

Example 49 Solubility of Various HS-CAB's

The HS-CAB's described in Tables 2-3 (Examples 1-27) are treated withsolvents and solvent blends (0.2 g of ester in 1.8 g of solvent) toprepare 10 wt % solutions of the CAB's and conventional CAB's(CAB-381-0.1 and CAB-551-0.01). The samples are placed on a rollerovernight to allow them to go into solution. Samples are removed fromthe roller and the solubility of each HS-CAB in each solvent or solventblend is determined according to the following criteria:

1=Insoluble; 3=Partially Soluble; 5=Gels; 7=Soluble, Hazy;

9=Soluble, Clear. The results of the solubility studies are presented inTables 17-19.

TABLE 17 CAB CAB CAB EMT02-105 EMT2-158 EMT03-030 EMT02-117 EMT02-162EMT02-131 171-15S 381-0.1 551-0.01 HS-CAB-55 HS-CAB-38 HS-CAB-38HS-CAB-55 HS-CAB-38 HS-CAB-55 Wt % Bu 53.88 39.51 35.01 54.1 39.73 54.59Wt % Ac 2.52 11.21 13.42 2.21 11.5 2.36 Wt % OH 1.09 2.16 3.51 1.19 1.133.1 Isopropyl 1 1 1 1 3 9 1 1 9 alcohol/ water 90/10 C-11 ketone 1 1 9 99 3 9 5 5 DIBK 1 1 9 9 7 3 9 9 9 PP 1 1 9 9 9 9 9 9 9 EP 1 1 9 9 9 9 9 99 EB 1 1 9 9 9 9 9 7 9 MeOH 1 1 1 1 9 9 3 3 9 Tescol C 1 1 1 3 1 3 3 1 9(95) Toluene 1 1 5 9 9 3 9 9 9 Xylene 1 1 1 1 1 1 1 1 1

TABLE 18 CAB CAB CAB EMT03-042 EMT03-059 EMT03-077 EMT03-051 EMT02-133171-15S 381-0.1 551-0.01 HS-CAB-20 HS-CAB-29 HS-CAB-46 HS-CAB-29HS-CAB-55 Wt % Bu 21.71 28.72 47.36 29.38 51.82 Wt % Ac 23.93 17.17 6.4418.37 2.85 Wt % OH 1.32 3.83 2.23 1.81 2.49 Isopropyl 1 1 1 1 3 9 1 9alcohol/ water 90/10 C-11 ketone 1 1 9 1 1 9 1 9.1 DIBK 1 1 9 1 1 9 1 .1PP 1 1 9 5 5 9 7 9.9 EP 1 1 9 9 1 9 9 9.9 EB 1 1 9 3 9 9 3 9.9 MeOH 1 11 1 9 9 1 9.9 Tescol C 1 1 1 1 1 9 1 9.9 (95) Toluene 1 1 5 3 1 9 1 9.1Xylene 1 1 1 1 1 1 1 1.1

TABLE 19 CAB CAB CAB EMT03-039 EMT03-044 EMT02-169 EMT03-062 EMT03-040171-15S 381-0.1 551-0.01 HS-CAB-20 HS-CAB-20 HS-CAB-55 HS-CAB-46HS-CAB-20 Wt % Bu 24.25 22.87 45.39 44.18 23.99 Wt % Ac 21.12 27.45 3.567.24 21.43 Wt % OH 2.31 0.81 4.61 3.1 3.23 Isopropyl 1 1 1 1 1 9 9 1alcohol/water 90/10 C-11 ketone 1 1 9 1 1 9 5 1 DIBK 1 1 9 1 1 3 3 1 PP1 1 9 5 7 9 9 5 EP 1 1 9 9 1 9 9 9 EB 1 1 9 3 3 9 9 3 MeOH 1 1 1 1 1 9 91 Tescol C (95) 1 1 1 1 1 9 9 1 Toluene 1 1 5 3 3 3 3 3 Xylene 1 1 1 1 13 1 1 Esters EMT02-105 EMT2-158 EMT03-030 EMT02-117 EMT02-162 EMT02-131EMT03-042 HS-CAB-55 HS-CAB-38 HS-CAB-38 HS-CAB-55 HS-CAB-38 HS-CAB-55HS-CAB-20 Isopropyl alcohol/ 1 3 9 1 1 9 1 water 90/10 C-11 ketone 9 9 39 5 5 1 DIBK 9 7 3 9 9 9 1 PP 9 9 9 9 9 9 5 EP 9 9 9 9 9 9 9 EB 9 9 9 97 9 3 MeOH 1 9 9 3 3 9 1 Tescol C (95) 3 1 3 3 1 9 1 Toluene 9 9 3 9 9 93 Xylene 1 1 1 1 1 1 1 n-butyl acetate 9 9 9 9 9 9 7 Ethyl acetate 9 9 79 9 9 7 Texanol 9 9 9 9 9 9 3 2-EH acetate 9 9 3 9 9 9 1 EEP 9 9 7 9 9 97 PM 9 9 9 9 9 9 7 PB 9 9 9 9 9 9 7 PM acetate 9 9 9 9 9 9 7 EB acetate9 9 9 9 9 9 7 MPK 9 9 7 9 9 9 7 MEK 9 9 9 9 9 9 7 MAK 9 9 9 9 9 9 7Acetone 9 9 9 7 9 9 9 Esters EMT03-059 EMT03-077 EMT03-051 EMT02-133EMT03-039 EMT03-044 EMT02-169 HS-CAB-29 HS-CAB-46 HS-CAB-29 HS-CAB-55HS-CAB-20 HS-CAB-20 HS-CAB-55 Isopropyl alcohol/ 3 9 1 9 1 1 9 water90/10 C-11 ketone 1 9 1 9 1 1 9 DIBK 1 9 1 1 1 1 3 PP 5 9 7 9 5 7 9 EP 19 9 9 9 1 9 EB 9 9 3 9 3 3 9 MeOH 9 9 1 9 1 1 9 Tescol C (95) 1 9 1 9 11 9 Toluene 1 9 1 9 3 3 3 Xylene 1 1 1 1 1 1 3 n-butyl acetate 9 9 7 9 57 9 Ethyl acetate 9 9 9 9 7 7 9 Texanol 3 9 9 9 7 1 9 2-EH acetate 1 9 19 1 1 3 EEP 9 9 7 9 7 7 9 PM 9 9 9 9 7 7 9 PB 9 9 9 9 7 7 9 PM acetate 99 9 9 9 7 9 EB acetate 9 9 9 9 9 7 9 MPK 9 9 9 9 7 7 7 MEK 9 9 9 9 9 7 9MAK 5 9 7 9 7 7 9 Acetone 9 9 9 9 9 9 9 Esters EMT03- EMT03- 062 040Isopropyl 9 1 alcohol/water 90/10 C-11 ketone 5 1 DIBK 3 1 PP 9 5 EP 9 9EB 9 3 MeOH 9 1 Tescol C (95) 9 1 Toluene 3 3 Xylene 1 1 n-butyl acetate9 5 Ethyl acetate 9 7 Texanol 9 7 2-EH acetate 5 1 EEP 9 7 PM 9 9 PB 9 7PM acetate 9 9 EB acetate 9 9 MPK 9 7 MEK 9 9 MAK 9 9 Acetone 9 9

Example 50

Inventive HS-CAB-17 and HS-HS-CAB-38 esters are evaluated as pigmentgrinding vehicles for inks or coating. Eight millbases and eight inkformulations are prepared as described in Table 20. Compared toconventional CAB grades, color development (color strength) of inventiveHS-CAB's is equal or better.

TABLE 20 291-1 291-2 291-3 291-4 291-5 291-6 291-7 291-8 MillbasesCAB-381-0.1 Solution (290-1) 25 25 HS-CAB-38 Solution (290-2) 25 25CAB-171-15 Solution (290-5) 25 25 HS-CAB-20 Solution (290--6) 25 25 Blue15:3 Pigment (Aarbor) 25 25 25 25 VT8015 Violet Pigment (Uhlich) 25 2525 25 Ethanol/Ethyl Acetate (70:30) Blend 50 50 50 50 EthylAcetate/Ethanol (70:30) Blend 50 50 50 50 Total 100  100  100  100  100 100  100  100  INKS Millbases 50 50 50 50 50 50 50 50 CAB-381-0.1Solution (290-1) 35 50 HS-CAB-38 Solution (290-2) 35 35 CAB-171-15Solution (290-5) 35 35 HS-CAB-20 Solution (290-6) 35 35 Ethanol/EthylAcetate (70:30) Blend 15 15 15 15 Ethyl Acetate/Ethanol (70:30) Blend 1515 15 15 Total 100  100  100  100  115  100  100  100  Color Strength(bleached white, %) 100  100  100  100  80 100  80 100  Transparency onLeneta (RK #2)  1  1  1  1  3  2  1  1 Gloss @ 60 on Leneta White (RK#2)  6   1.2   1.4   1.1 36 40 32 23 Gloss @ 60 on C1S  7   1.4   1.4  0.7 34 37 31 32 Adhesion on Leneta Black  5  1  4  1  5  2  5  2Adhesion on Leneta White  5  2  3  2  5  2  1  2 Adhesion on PP  4  2  1 2  4  1  1  3 Adhesion on White PE  1  3  1  2  1  2  1  3 BlockResistance (F.) @ 40 psi, 1 sec on C1S 270  230  400+ 400+ 270  230 400+ 400+ Water Resistance on PP  5  5  5  5  5  4  5  5 WaterResistance on White PE  5  3  5  5  5  3  5  5 Alcohol Resistance on PP 1  1  1  1  1  1  1  1 Alcohol Resistance on White PE  1  1  1  1  1  1 1  1 Alkali Resistance on PP  5  5  5  5  5  4  5  5 Alkali Resistanceon White PE  5  1  5  5  5  2  5  4 409 Resistance on PP  5  5  4  1  5 3  3  4 409 Resistance on White PE  4  3  1  1  2  1  5  1 Rating: 1 =Poor; 5 = Excellent Samples are ranked relative to a standard.

Example 51 Improved Melt Stability of HS-CAB's

An inventive HS-CAB-38, having a glass transition temperature (T_(g)) of89° C. and a melt temperature of 120° C., is placed on a preheated2-roll horizontal mill (80° C.). The HS-CAB powder adheres to the Rolland the temperature is gradually increased until the HS-CAB begins tosoften and flow (˜100° C.). It is noted that this material appears tohave good thermal stability. After nearly 30 minutes on the mill, theCAB has not yellowed.

Example 52 HS-CAP-48: High Propionyl, Low DP CAP

A 2 L-reaction kettle was charged with a propionic acid-wet activatedcellulose (311.77 g total, 160 g dry cellulose), prepared according toExample 1, except that the butyric acid wash was replaced with apropionic acid wash. Propionic acid (262.5 g) and acetic acid (5.22 g)were added to the kettle. The mixture was cooled to −10° C. A mixture ofpropionic anhydride (757.69 g) and sulfuric acid (5.44 g) were cooled to−30° C. and then added to the reaction kettle. The mixture was stirredfor 1 hour at room temperature. The mixture was then heated to 70° C.Sulfuric acid (5.44 g) was added to the clear dope approximately 1 hourafter the room temperature hold. The mixture was then stirred at 70° C.and stirred for 3 hours and 52 minutes. A mixture of water (182.5 g) andacetic acid (498.4 g) was slowly added to the clear “dope.” The mixturewas stirred for 24 hours at 70° C. The catalyst was neutralized by theaddition of Mg(OAc)₄ (14.1 g) dissolved in HOAc (475 g) and water (195g). The neutralized dope was filtered at approximately 50° C. through aglass wool-covered coarse fritted funnel. The product was precipitatedby pouring, with rapid mixing, the clear, neutralized dope into 20-30volumes of water. Decanting away the filtration liquid and adding freshdeionized water and then allowing the precipitate to stand in the freshwater for several hours hardened the precipitate. The precipitate waswashed extensively with deionized water for at least 2 hours. Theproduct was dried in a vacuum oven at approximately 50° C. overnight.The product had the following composition: DS_(Pr)=1.75; DS_(Ac)=0.22;M_(n)=3887; M_(w)=7036; Polydispersity=1.81; IV (PM95)=0.086.

Example 53 Coating Formulations with HS-CAB-38 and Evaluation

Clearcoat formulations are prepared according to Tables 21-22 and theresulting coatings are evaluated to determine the effect differentlevels of HS-CAB-38 (Sample 4, Table 4) have on dry-to-touch time,hardness development, and gloss.

TABLE 21 Solvent Blend n-Butyl Acetate 66.0 Xylene 34.0 Total 100.0

TABLE 22 Formulations with HS-CAB-38 2% 4% 8% 0% CAB CAB CAB CABSynocure 851 S (60%) (Xylene: 48.8 48.5 47 46 n-Butyl Acetate) (2:1)HS-CAB-38 (50%) (n-Butyl Acetate) — 1.2 2.3 4.8 Eastman EEP⁽¹⁾ 4.1 4 3.93.8 Solvent blend 27.4 26.6 27.5 26.3 Desmodur N 75 BA (75%) 19.7 19.719.3 19.1 (n-Butyl Acetate) Total 100 100 100 100 DIN 4 viscosity(seconds) 19.5 19.7 19.2 19.5 Theoretical % Total Solids Content 44.144.5 43.8 44.3 ⁽¹⁾Ethyl 3-ethoxypropionate Synocure 851 S: 4.5% OHcontentDry-To-Touch Time

Coatings re prepared (Tables 21-22) with an OH:NCO stoichiometry of 1:1,and a DIN 4 viscosity of 18-20 seconds. Coatings are prepared with 0%CAB and with 2%, 4% and 8% of the hydroxy-functional acrylic substitutedwith the HS-CABs. Each of the coatings is spray applied to ChemetallGold Seal, high zinc phosphate 1.0 mm steel panels using a DeVilbiss JGA545 spray gun at 55 psi air pressure. Three panels are coated for eachtest ratio, such that a range of dry film thickness including 45 μm isobtained. The dry-to-touch time is evaluated by a thumb print test(according to ASTM D 1640 section 7.4.2).

TABLE 23 Dry-To-Touch Time (Minutes) Example # 0% CAB 2% CAB 4% CAB 8%CAB 53 HS-CAB-38 230 207 184 180

The results of the dry-to-touch times are shown in Table 23. Theshortest dry-to-touch times are achieved as the level of HS-CAB-38(Sample 4, Table 4) is increased.

Hardness Development

Each of the panels is also assessed for hardness development by Königpendulum hardness evaluations. Tests are carried out after 24 hours andcontinued every 24 hours up to 168 hours. The panels are stored at 23°C. during this period.

TABLE 24 Hardness Development with HS-CAB-38, König Pendulum Hardness(Seconds) Hours 0% CAB 2% CAB 4% CAB 8% CAB 24 23 22 21 21 48 71 68 6770 72 104 101 99 103 144 143 139 140 142 168 183 180 182 184

König pendulum hardness results are shown in Table 24. After 24 hoursand at the end of the 7 days test period, the HS-CAB-38 content of eachset of coatings has little effect on the König pendulum hardness.

Example 54 HS-CABs as Flow Additives in Automotive MonocoatFormulations: General Formulations

A white-pigmented high solids coating using a hybridacrylic-isocyanate-polyester system is developed which can be sprayed at70% solids and 18 second Ford Cup #4 viscosity (Tables 25 and 26). Anultra high solids master batch consisting of TRONOX CR828 (titaniumdioxide pigment), Rohm and Haas AU608X (acrylic polyol), andSherwin-Williams US-2 solvent (paint thinner) are mixed together underhigh shear. To this, CAB, BYK® 325, or a combination of the two areadded along with the isocyanate portion, (Bayer Desmodur N 3300) andBayer Desmophen 800 (polyester polyol) used to keep the OH/CN balance.The Brookfield viscosities are measured at the same solids prior to theaddition of the isocyanate. After the isocyanate is added, the sprayviscosities are adjusted with the addition of Sherwin-Williams US-2thinner to 18-20 second Ford Cup #4 and sprayed using a DeVibliss airassisted spray gun at 35 pounds of pressure. Two panels of eachformulation are sprayed. After flash-off for 40 minutes at roomtemperature, the panels are baked in an oven at 82° C. (180° F.) for 30minutes. Before any of the panels are tested, the baked panels are laidhorizontally in a constant temperature-humidity room at 24° C. (70° F.)and 50% relative humidity for 7 days.

TABLE 25 Pigment Dispersion Rohm and Haas AU608X (OH Functional Acrylic)41.42 TRONOX 828 (Titanium Dioxide Pigment) 56.66 Sherwin Williams US-2Thinner 1.92

The pigment dispersion is mixed in an Eiger High Speed Disperser untilthe particle size is <0.1 micron on a Hegmann gauge. This is achieved bymixing at 300 rpm for 5 minutes, allowing the solution to cool andrepeating 5 times.

TABLE 26 5 formulations with 4 types of cellulose esters B: No CAB/ C:With D: With ½ E: With A: No CAB/ With CAB/No CAB/With ½ CAB/With NoBYK ® 325 BYK ® 325 BYK ® 325 BYK ® 325 BYK ® 325 Bayer 15.04 15.0415.04 15.04 15.04 Desmodur N 3390 Pigment 57.84 57.84 57.84 57.84 57.84Dispersion (II above) US-2 Thinner 12.75 12.75 9.08 10.91 9.08 Bayer14.37 14.37 10.70 12.53 10.70 Desmophen 800 CAB (50 wt % 0 0 7.34 3.677.34 solution BYK ® 325 0 0.50 0 .25 0.5 Total 100.00 100.50 100.00100.25 100.50 Two panels are sprayed for each paint type (Table26-Columns A, B, C, E) along with center point replicates, (formulation26-D paints). The samples are tested for pencil hardness¹, pendulumrocker hardness (König),² Tukon Hardness (Knoops), orange peel,smoothness, gloss by wave guide measurements (long and short waves),gloss at 20 degrees and 60 degrees,³ distinctness of image (DOI),⁴experimental solids, Brookfield viscosity,⁵ Ford Cup viscosity, MEKDouble Rubs,⁶ thickness,⁷ tape pull adhesion tests,⁸ and a visualinspection for pinholes and craters. ¹ASTM Method D3363-00, “StandardTest Method for film hardness by pencil test.” ²ASTM Method D4366-95,“Standard Test Methods for hardness of Organic Coatings by PendulumDamping Tests.” ³ASTM Method D523-89 (1999), “Standard Test Method forSpecular Gloss.” ⁴ASTM Method D5767-95 (1999), “Standard Test Methodsfor Instrumental Measurement of Distinctness-of-Image Gloss of CoatingSurfaces.” ⁵ASTM Method D2196, “Test Methods for Rheological Propertiesof Non-Newtonian Materials by Rotational (Brookfield) Viscometer.” ⁶ASTMMethod 5402, “Practice of Assessing the Solvent Resistance of OrganicCoatings Using Solvent Rubs.” ⁷ASTM Method D1186, “Test Method forNondestructive Measurement of Dry film thickness of Nonmagnetic CoatingApplied to a Ferrous Base.” ⁸ASTM Method D3359, “Test Methods forMeasuring Adhesion by Tape Test.”

HS-CAB-55 (Sample 5, Table 4) and HS-CAB-38 (Sample 4, Table 4) providethe same anti-cratering, anti-mounding and anti-pinholing property asCAB-381-0.1 and CAB-551-0.01 yet at much higher application solids. Allthe panels which do not contain cellulose ester have pinholes orcraters. HS-CAB-55 and HS-CAB-38 do not hurt the adhesion of paint tothe substrate. Furthermore, HS-CAB-38 and HS-CAB-55 do not hurt Tukonhardness, as no samples are found to be significantly worse than others.20 and 60 degree Specular Gloss are not hurt by the addition ofHS-CAB-38 or HS-CAB-55. The addition of CAB-381-0.1 hurts 20 degreegloss values when compared to all other samples. Gloss by short-waveWave-Scan measurements indicate that HS-CAB-38 and HS-CAB-55 are thesmoothest samples. They are considerably better than standard celluloseesters yet the solids are much higher.

Examples 55-59 Pigmented Thermoplastic Automotive Basecoat

HS-CAB-17 (Sample 3, Table 4) and HS-CAB-38 (Sample 1, Table 4) areevaluated as metallic flake control agents in a high solids basecoatuseful for automotive coatings. Five formulations are prepared asdescribed in Table 27. The formulations are sprayed onto metal panelsusing a spray technique altered to accommodate for the higher solids.The formulations are reduced with xylene/n-BuOAc to obtain the samesolids level as Example 55 (i.e. 69%). Example 55 contains HS-CAB-17,Example 56 contains HS-CAB-38, Example 57 (Comparative) is the controland contains no metallic flake control agent, and Examples 58 and 59contain the microgel metallic flake control agent R-1623-M3.

TABLE 27 Example # 55 56 57 58 59 HS-CAB-17 (60%)⁹ 30 0 0 0 0 HS-CAB-38(60%)¹⁰ 0 30 0 0 0 Coroc R-1623-M3 0 0 0 10 10 Reactol 175 (80%) 20 2050 50 60 Cymel 301 20 20 20 20 20 Stapa Metalux 20 20 20 20 20 Mica 2 22 2 13 EEP 8 8 8 0 2 Total 100 100 100 102 126 Panel Appearance¹¹Excellent Fair Poor Poor Good Adjusted Appearance NA NA Good Good NA⁹60% solids in MEK, Batch EMT02-085 ¹⁰60% solids in MEK, Batch EMT02-113¹¹When sprayed at 69% solids

Excellent appearance is achieved at a solids level of 69% weight solidscompared to a commonly used control of 52% weight solids. Example 55exhibits excellent appearance and good holdout from the OEM clear. Thecoating also exhibits good travel or flop. The appearance is poor withExamples 57-59 when sprayed at 69% solids. The appearance of Example 56is fair.

Further reduction is done with the control formulations and theformulations containing the microgels until a good appearance isobtained. For example, the amount of solids for Example 57 is 52.4 inorder to obtain similar appearance as Example 55.

Once basecoats with approximately equal appearance are prepared, onehalf of each panel is then sprayed with a commercial 2-componenturethane clearcoat, DuPont OEM TSA, and baked at 121° C. (250° F.) for20 minutes. Flop/Travel is measured for each cured panel (see Table 28).Example 55 (HS-CAB-17) has good appearance and travel, Example 59 (noCAB or microgel) has good appearance and fair travel when reduced to52.4% solids, and Example 59 (HS-CAB-38) has fair appearance and poortravel, indicating that there is “strike in” of the basecoat by thetopcoat solvents.

TABLE 28 Example # Notebook # Additive Flop/Travel % Solids 55X-19870-16 HS-CAB-17 12.22 69 58 X-19870-18 R-1623-3M 10.67 54 56X-19870-20 HS-CAB-38 10.25 69

Example 60 Low Molecular Weight CAB's In Urethane Clearcoat Formulation

A new CAB/Acrylic/Urethane formulation is developed loosely based on acombination of two Eastman Publications (E-321 & TT-96-SOL-2A). Thepurpose of this new formulation is to show the improved flow propertiesand quicker dry-to-touch time of acrylic isocyanate formulation whenCAB-551-0.01 is added. Then, determine if the HS-CAB will give similarimprovements without contributing as greatly to viscosity.

The following formulations are prepared:

TABLE 29 Without CAB With CAB (grams) (grams) 70.93 53.89 Rohm & HaasParaloid AU-608B Acrylic (60% solids in n-Butyl Acetate) 0.00 23.52 CAB(50% solution in acetone) 0.45 7.27 n-Butyl Acetate 11.76 0.00 Acetone0.59 0.59 Dibutyltin Dilaurate (DBTDL) catalyst (1% in n-Butyl Acetate)16.26 14.73 Bayer Desmodur N-100 Aliphatic Isocyanate (100% Solids)100.00 100.00 Total Formulation Constants 58.8 wt. % SolidsAcrylic/CAB/Isocyanate Ratio 55/20/25 41.2 wt % solvent 71.5% n-ButylAcetate, 28.5% Acetone Isocyanate/Polyol Ratio 1.2/1 DBTDL catalystlevel 0.01% based on solids

Examples 61-66 Evaluation of HS-CAB-38 in Urea Formaldehyde Coatings

A series of formulations containing HS-CAB (Sample 4, Table 4), at 4different levels), CAB-381-0.1, and no CAB, are prepared as described inTable 30. Table 36 shows the viscosity of the systems at 22.3% solidsfor the CAB-381-0.1 and 24.3% solids for the rest. The use of HS-CAB-38gives formulations with viscosities approximately one tenth that offormulations using the CAB-381-0.1 control and one third that of thecontrol without CAB. The HS-CAB-38 samples are applied at a solids levelof 40%, approximately twice that of the controls.

The samples are spray applied and allowed to cure for one week prior toevaluation. All samples pass chemical resistance tests with greater than200 MEK double rubs.

The results of both forward and reverse impact are listed in Table 36.Forward impact drops with the initial change in ratio of the acrylicpolyol to HS-CAB-38 but does not change with subsequent alterations.Reverse impact is poor in all cases with no notable differences.

Table 31 also lists the 60° gloss for each example. Gloss is not reducedappreciably even at high levels of HS-CAB-38. The one exception is the25:45 ratio of AU608X to HS-CAB-38. This sample yields values that areup to 9 points lower.

Crosshatch adhesion is 100 percent retained with all samples.

In this evaluation the HS-CAB-38 samples in all ratios yield higherhardness values than do CAB-381-0.1.

TABLE 30 Formulations of HS-CAB-38/Urea Formaldehyde Coatings Ex. #61Ex. #62 Ex. #63 Ex. #64 Ex. #65 Ex. #66 Paraloid 28.2 16.6 18.2 14.1 100 AU608X Cymel U80 7.2 6.5 7.2 7.2 7.2 7.2 CAB-381-0.1 0 18.2 0 0 0 0HS-CAB-38 0 0 6 8.5 10.8 16.9 n-Butyl Acetate 38.4 34.9 40.8 41.8 42.845.2 Xylene 25.7 23.3 27.3 27.9 28.7 30.2 pTSA^(A) 0.5 0.4 0.5 0.5 0.50.5

TABLE 31 Evaluation of HS-CAB-38/Urea Formaldehyde Coatings Ex. # 61 Ex.# 62 Ex. # 63 Ex. # 64 Ex. # 65 Ex. # 66 Wt. % Solids 24.3 22.3 24.324.3 24.3 24.3 Viscosity cP of above 18.5 56.8 7.3 5.5 5 4 solidsApplication solids 24.3 22.3 40 40 40 40 MEK DoubleRubs >200 >200 >200 >200 >200 >200 Impact Forward (psi) 30 30 30 20 2020 Impact Reverse (psi) <10 <10 <10 <10 <10 <10 Gloss 93 91 92 92 84 90Adhesion 100 100 100 100 100 100 König 195 178 180 186 184 184

In the drawings and specification, there have been disclosed typicalpreferred embodiments of the invention and, although specific terms areemployed, they are used in a generic and descriptive sense only and notfor purposes of limitation, the scope of the invention being set forthin the following claims.

1. A cellulose mixed ester having the following properties: a totaldegree of substitution per anhydroglucose unit of from 3.08 to 3.50,having the following substitutions: a degree of substitution peranhydroglucose unit of hydroxyl of no more than about 0.70, a degree ofsubstitution per anhydroglucose unit of C₃-C₄ esters from about 0.80 toabout 1.40, and a degree of substitution per anhydroglucose unit ofacetyl of from about 1.20 to about 2.34; an inherent viscosity of from0.05 to 0.12 dL/g, as measured in a 60/40 (wt./wt.) solution ofphenol/tetrachloroethane at 25° C.; a number average molecular weight(M_(n)) of from about 1,000 to about 5,600; a weight average molecularweight (M_(w)) of from about 1,500 to about 10,000; and a polydispersityof from about 1.2 to about 3.5.
 2. The cellulose mixed ester accordingto claim 1, wherein the C₃-C₄ ester comprises butyryl, and wherein thecellulose mixed ester forms a clear solution as a 10 weight percentmixture in propylene glycol monomethyl ether.
 3. The cellulose mixedester according to claim 1, wherein the C₃-C₄ ester comprises butyryl,and wherein the cellulose mixed ester forms a clear solution as a 10weight percent mixture in propylene glycol methyl acetate.
 4. Thecellulose mixed ester according to claim 1, wherein the C₃-C₄ estercomprises butyryl, and wherein the cellulose mixed ester forms a clearsolution as a 10 weight percent mixture in diethylene glycol methylether.
 5. The cellulose mixed ester according to claim 1, wherein theC₃-C₄ ester comprises propionyl.
 6. The cellulose mixed ester accordingto claim 1, wherein the degree of substitution per anhydroglucose unitof hydroxyl is from about 0.05 to about 0.70.
 7. The cellulose mixedester according to claim 1, wherein the number average molecular weight(M_(n)) is from about 1,500 to about 5,000.
 8. The cellulose mixed esteraccording to claim 1, wherein the polydispersity is from 1.2 to 2.5. 9.The cellulose mixed ester according to claim 1, wherein the inherentviscosity is from 0.07 to 0.11 dL/g.
 10. The cellulose mixed esteraccording to claim 1, wherein the number average molecular weight(M_(n)) is from about 1,000 to about 4,000.
 11. The cellulose mixedester according to claim 1, wherein the C₃-C₄ ester comprises butyryl,and wherein the cellulose mixed ester exhibits a viscosity no greaterthan 6,000 centipoise as a 50 wt. % solution in a 90/10 by weightmixture of n-butyl acetate/xylene.
 12. The cellulose mixed esteraccording to claim 1, wherein the C₃-C₄ ester comprises butyryl, andwherein the cellulose mixed ester exhibits a viscosity no greater than3,000 centipoise as a 50 wt. % solution in a 90/10 by weight mixture ofn-butyl acetate/xylene.
 13. A cellulose mixed ester having the followingproperties: a total degree of substitution per anhydroglucose unit offrom 3.08 to 3.50, having the following substitutions: a degree ofsubstitution per anhydroglucose unit of hydroxyl of no more than about0.70; a degree of substitution per anhydroglucose unit of C₃-C₄ estersfrom about 1.40 to about 2.45, and a degree of substitution peranhydroglucose unit of acetyl of from about 0.20 to about 0.80; aninherent viscosity of from 0.05 to 0.12 dL/g, as measured in a 60/40(wt./wt.) solution of phenol/tetrachloroethane at 25° C.; a numberaverage molecular weight (M_(n)) of from about 1,000 to about 5,600; aweight average molecular weight (M_(w)) of from about 1,500 to about10,000; and a polydispersity of from about 1.2 to about 3.5.
 14. Thecellulose mixed ester according to claim 13, wherein the C₃-C₄ estercomprises butyryl, and wherein the cellulose mixed ester forms a clearsolution as a 10 weight percent mixture in C-11 ketone.
 15. Thecellulose mixed ester according to claim 13, wherein the C₃-C₄ estercomprises butyryl, and wherein the cellulose mixed ester forms a clearsolution as a 10 weight percent mixture in diisobutyl ketone.
 16. Thecellulose mixed ester according to claim 13, wherein the C₃-C₄ estercomprises butyryl, and wherein the cellulose mixed ester forms a clearsolution as a 10 weight percent mixture in propylene glycol monopropylether.
 17. The cellulose mixed ester according to claim 13, wherein theC₃-C₄ ester comprises butyryl, and wherein the cellulose mixed esterforms a clear solution as a 10 weight percent mixture in ethylene glycolmonopropyl ether.
 18. The cellulose mixed ester according to claim 13,wherein the C₃-C₄ ester comprises butyryl, and wherein the cellulosemixed ester forms a clear solution as a 10 weight percent mixture inethylene glycol monobutyl ether.
 19. The cellulose mixed ester accordingto claim 13, wherein the C₃-C₄ ester comprises butyryl, and wherein thecellulose mixed ester forms a clear solution as a 10 weight percentmixture in methanol.
 20. The cellulose mixed ester according to claim13, wherein the C₃-C₄ ester comprises butyryl, and wherein the cellulosemixed ester forms a clear solution as a 10 weight percent mixture inethanol with 5% water, containing methanol, methyl isobutyl ketone, andethyl acetate as denaturants.
 21. The cellulose mixed ester according toclaim 13, wherein the C₃-C₄ ester comprises butyryl, and wherein thecellulose mixed ester forms a clear solution as a 10 weight percentmixture in toluene.
 22. The cellulose mixed ester according to claim 13,wherein the C₃-C₄ ester comprises butyryl, and wherein the cellulosemixed ester forms a clear solution as a 10 weight percent mixture in a90/10 by weight isopropyl alcohol/water blend.
 23. The cellulose mixedester according to claim 13, wherein the C₃-C₄ ester comprisespropionyl.
 24. The cellulose mixed ester according to claim 13, whereinthe degree of substitution per anhydroglucose unit of hydroxyl is fromabout 0.05 to about 0.70.
 25. The cellulose mixed ester according toclaim 13, wherein the number average molecular weight (M_(n)) is fromabout 1,500 to about 5,000.
 26. The cellulose mixed ester according toclaim 13, wherein the polydispersity is from 1.2 to 2.5.
 27. Thecellulose mixed ester according to claim 13, wherein the number averagemolecular weight (M_(n)) is from about 1,000 to about 4,000.
 28. Thecellulose mixed ester according to claim 13, wherein the C₃-C₄ estercomprises butyryl, and wherein the cellulose mixed ester exhibits aviscosity no greater than about 500 centipoise as a 50 wt. % solution ina 90/10 by weight mixture of n-butyl acetate/xylene.
 29. A coatingcomposition, comprising: a) the cellulose mixed ester according to claim1 or 13; b) one or more coating resins; and c) one or more solvents. 30.A coating composition comprising: a) about 0.1 to about 50 weightpercent, based on the total weight of (a) and (b) in the coatingcomposition, of the cellulose ester according to claim 1 or 13; b) about50 to 99.9 weight percent, based on the total weight of (a) and (b) inthe composition, of at least one resin selected from the groupconsisting of a polyester, a polyester-amide, a cellulose ester, analkyd, a polyurethane, an epoxy resin, a polyamide, an acrylic, a vinylpolymer, a polyisocyanate, and a melamine; and c) at least one solvent;wherein the total weight of (a) and (b) is from about 5 to about 85weight percent of the total weight of (a), (b), and (c).
 31. The coatingcomposition according to claim 30, further comprising about 0.1 to about15 weight percent, based on the total weight of the composition, of oneor more coatings additives selected from the group consisting ofleveling, rheology, and flow control agents; flatting agents; pigmentwetting and dispersing agents; surfactants; ultraviolet (UV) absorbers;UV light stabilizers; tinting pigments; defoaming and antifoamingagents; anti-settling, anti-sag and bodying agents; anti-skinningagents; anti-flooding and anti-floating agents; fungicides andmildewcides; corrosion inhibitors; thickening agents; or coalescingagents.
 32. The coating composition of claim 31, further comprising oneor more fillers and/or pigments.
 33. The coating composition of claim32, wherein the pigment is comprised of aluminum or mica.
 34. A shapedor formed article coated with the composition of claim
 30. 35. A plasticmaterial coated with the composition according to claim
 30. 36. A metalcoated with the composition according to claim
 30. 37. A wood surfacecoated with the composition according to claim
 30. 38. A paper coatedwith the composition according to claim
 30. 39. A pigment dispersion,comprising: about 20 to about 50 weight percent by weight of a pigment;and about 50 to about 80 percent by weight of the cellulose mixed esterof claim 1 or
 13. 40. The pigment dispersion of claim 39, wherein thepigment is comprised of alumina or mica.
 41. A radiation curable coatingcontaining the cellulose mixed ester according to claim 1 or
 13. 42. Apowder coating containing the cellulose mixed ester according to claim 1or
 13. 43. An ink composition containing the cellulose mixed esteraccording to claim 1 or 13.